High-biological-activity polyether-ether-ketone material and preparation method thereof
By pretreating polyether ether ketone materials, forming high-temperature carbonization on the surface and depositing coatings on their surface, the bioinergic problem of polyether ether ketone materials is solved, high biological activity and bone integration effects are achieved, and the osteogenesis needs of clinical implants are met.
Patent Information
- Application Number
- CN202411854565.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-03-14
AI Technical Summary
The polyether ether ketone material has a smooth and hydrophobic surface, showing strong bioinergicity, which is not conducive to cell adhesion and bone integration, resulting in poor osteogenesis ability of the implant and easily lead to clinical implant failure.
By pretreating polyether etherketone, high-temperature surface carbonization treatment, forming porous structure carbonization layers, and depositing carbide, metal or bioceramic coatings on its surface, the residual surface stress is eliminated and biocompatibility and cell adhesion ability are improved.
The high biological activity of polyether ether ketone material is achieved, the cell attachment, proliferation and differentiation ability is enhanced, the bone integration is promoted, and the osteogenesis needs of clinical implants are met.
Smart Images
Figure CN119613785A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymer materials, and in particular to a polyetheretherketone material with high biological activity and a preparation method thereof. Background Art
[0002] The surface of polyetheretherketone material is smooth and hydrophobic, showing strong biological inertness, which is not conducive to cell adhesion. When used as an implant, it has poor osteogenic ability and poor bone integration, which can easily lead to clinical implant failure. Surface modification can improve the biological inertness of polyetheretherketone while ensuring mechanical properties, which is conducive to the attachment, proliferation and differentiation of osteoblasts and promotes bone integration. It is a very economical and effective method to improve the biological activity of materials and meet the evolving clinical needs. Summary of the invention
[0003] The technical solution of the present invention is a method for preparing a polyetheretherketone material with high biological activity, the preparation method comprising the following steps: 1) Pre-treat the polyetheretherketone, clean the surface and remove the surface burrs; 2) subjecting the pretreated polyetheretherketone to surface high-temperature treatment to carbonize the surface of the polyetheretherketone to form a porous carbonized layer having a porous structure; 3) performing surface deposition treatment on the modified polyetheretherketone obtained in step 2), directly depositing a carbide coating on the surface of the porous structure carbonized layer, or depositing a metal coating, a bioceramic coating or a polymer coating on the surface of the porous structure carbonized layer; 4) Post-treating the modified polyetheretherketone obtained in step 3) to eliminate surface residual stress, thereby obtaining a polyetheretherketone material with high biological activity.
[0004] Preferably, the pretreatment in step 1) is to use compressed air to remove surface burrs, dust and other pollutants.
[0005] Compressed air parameters: processing time: 1min, processing temperature: room temperature, pressure: 12bar, flow rate: 100L / min Preferably, the surface carbonization treatment technology in step 2) includes: laser treatment, plasma surface treatment, electron beam surface heat treatment, arc treatment or corona discharge treatment.
[0006] The porous carbonized layer in step 2) has a thickness of 5-100 μm, a porosity of 20-80%, a pore size of 20-50 μm, and a specific surface area of 1.5-4.5 m2 / g.
[0007] Preferably, in step 2), the surface carbonization treatment is followed by surface high-frequency heat treatment.
[0008] The parameters of surface high frequency heat treatment are: current frequency 50-100KHz.
[0009] Surface high-frequency heat treatment can refine the surface carbon particles and improve the bonding force between the coating and the carbon layer.
[0010] Preferably, the porous carbonized layer of the modified polyetheretherketone material obtained after the high-temperature surface treatment in step 2) has excellent biocompatibility. At the same time, the surface carbonized layer is a porous structure, which is conducive to cell growth and can provide sufficient oxygen and nutrients for new cells, so it can be directly used as an implant material.
[0011] Preferably, the process of directly depositing carbides on the surface of the porous carbonized layer in step 3) includes: cold spraying, chemical vapor deposition or electrophoretic deposition.
[0012] Preferably, the process of depositing metal on the surface of the porous carbonized layer in step 3) includes: DC magnetron sputtering, pulsed laser deposition, ion plating, chemical vapor deposition, cold spraying, metal transfer plating, plasma immersion ion implantation, microwave assisted coating or hybrid vacuum deposition.
[0013] Preferably, the process of depositing bioceramics on the surface of the carbonized layer in step 3) includes: cold spraying, magnetron sputtering or vacuum plasma spraying.
[0014] Preferably, the process of constructing the polymer coating on the surface of the carbonized layer in step 3) is a dip coating method or a spin coating method.
[0015] Preferably, the carbide directly deposited or the carbide generated by reaction with the metal in step 3) includes: titanium carbide, zirconium carbide, tantalum carbide, niobium carbide, tungsten carbide, molybdenum carbide, chromium carbide, manganese carbide, iron carbide or magnesium carbide.
[0016] More preferably, the carbide in step 3) includes: zirconium carbide, molybdenum carbide, manganese carbide, iron carbide or magnesium carbide.
[0017] Preferably, the bioceramic in step 3) comprises: hydroxyapatite, zirconium oxide or titanium oxide.
[0018] Preferably, the polymer material in step 3) includes: polylactic acid, polycaprolactone or chitosan.
[0019] Preferably, the thickness of the carbide coating, bioceramic coating and polymer coating in step 3) is 5-20 μm.
[0020] Preferably, the thickness of the overall carbide modified layer in step 3) is 10-120 μm.
[0021] The overall carbide modified layer includes a porous structure carbide layer and a carbide layer deposited on the surface of the porous structure carbide layer.
[0022] Preferably, the post-treatment in step 4) includes: stress relief annealing and tempering.
[0023] The beneficial effects of the present invention are as follows: the polyetheretherketone material with high bioactivity provided by the present invention has good biocompatibility and bioactivity, and can meet the clinical needs in the medical field.
[0024] Description of the drawings: Figure 1 It is the cell survival rate of the polyetheretherketone materials in Examples 1-18 and Comparative Examples 1-4 in Experimental Example 1 of the present invention. DETAILED DESCRIPTION
[0025] The present invention will be further described below in conjunction with embodiments. Example 1
[0026] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0027] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by electron beam surface heat treatment, so that the surface of the polyetheretherketone is carbonized, and the thickness of the formed carbonized layer is 5 μm.
[0028] 3) The modified polyetheretherketone obtained after the surface carbonization treatment is subjected to surface high-frequency heat treatment with a current frequency of 50 KHz.
[0029] 4) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by electrophoretic deposition, and a zirconium carbide modified layer is deposited on the surface of the carbide layer. The thickness of the overall carbide modified layer is 10 μm.
[0030] 5) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S1 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Example 2
[0031] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0032] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by electric arc treatment, so that the surface of the polyetheretherketone is carbonized, and the thickness of the formed carbonized layer is 100 μm.
[0033] 3) The modified polyetheretherketone obtained after the surface carbonization treatment is subjected to surface high-frequency heat treatment with a current frequency of 80 KHz.
[0034] 4) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by chemical vapor deposition, and a manganese carbide modified layer is deposited on the surface of the carbonized layer. The thickness of the manganese carbide modified layer is 120 μm.
[0035] 5) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S2 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 290°C, heat preservation for 1 hour, and then cooling with the furnace. Example 3
[0036] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0037] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone is carbonized, and the thickness of the formed carbonized layer is 20 μm.
[0038] 3) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by cold spraying, and iron carbide is deposited on the surface of the carbide layer to form an iron carbide modified layer; the thickness of the formed iron carbide modified layer is 35 μm.
[0039] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S3 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Example 4
[0040] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0041] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.1mm, scanning speed 60mm / s, power 2w. The thickness of the formed carbonized layer is 10μm.
[0042] 3) The modified polyetheretherketone obtained after the surface carbonization treatment is subjected to surface high-frequency heat treatment, with a current frequency of 100 KHz.
[0043] 4) The surface of the modified polyetheretherketone was treated with surface deposition by using DC magnetron sputtering technology, and tungsten metal was deposited on the surface of the carbide layer to form a tungsten carbide modified layer; the parameters used for DC magnetron sputtering were: working voltage 250V, working current 1A, vacuum degree 1.2Pa, and sputtering time 60min. The thickness of the formed tungsten carbide modified layer was 20μm.
[0044] 5) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S4 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 260°C, heat preservation for 1 hour, and then cooling with the furnace. Example 5
[0045] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0046] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.1mm, scanning speed 60mm / s, power 2w. The thickness of the formed carbonized layer is 30μm.
[0047] 3) The modified polyetheretherketone surface was treated with chemical vapor deposition technology to deposit tungsten metal on the surface of the carbide layer to form a tungsten carbide modified layer; the parameters used for DC magnetron sputtering were: working voltage 250V, working current 1A, vacuum degree 1.2Pa, sputtering time 60min. The thickness of the formed tungsten carbide modified layer was 35μm.
[0048] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S5 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 250°C, heat preservation for 1 hour, and then cooling with the furnace. Example 6
[0049] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0050] 2) The pretreated polyetheretherketone was subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone was carbonized to form a carbonized layer; the parameters of the plasma surface treatment were: discharge frequency 17kHz, voltage 2.5kV, gas flow 5slpm, action time 90s, distance 10mm. The thickness of the carbonized layer was 25μm.
[0051] 3) The surface of the modified polyetheretherketone was treated with pulsed laser deposition technology to deposit tantalum metal on the surface of the carbide layer to form a tantalum carbide modified layer; the parameters of the pulsed laser deposition technology were: pulse frequency 10 Hz, pulse energy during deposition 150 mj, deposition time 50 min. The thickness of the formed tantalum carbide modified layer was 30 μm.
[0052] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S6 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Example 7
[0053] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0054] 2) The pretreated polyetheretherketone was subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone was carbonized to form a carbonized layer; the parameters of the plasma surface treatment were: discharge frequency 17kHz, voltage 2.5kV, gas flow 5slpm, action time 90s, distance 10mm. The thickness of the carbonized layer was 60μm.
[0055] 3) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by using cold spraying technology, and magnesium metal is deposited on the surface of the carbide layer to form a magnesium carbide modified layer; the thickness of the formed magnesium carbide modified layer is 80 μm.
[0056] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S7 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 240°C, heat preservation 0.5h, and then cooling with the furnace. Example 8
[0057] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0058] 2) Electron beam surface heat treatment is used to treat the pretreated polyetheretherketone at high temperature, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer, thereby obtaining a polyetheretherketone material with high biological activity. The parameters of the electron beam surface heat treatment are: sweep voltage 40KV, current 15mA, vacuum degree 10 -2 Pa. The thickness of the formed carbonized layer was 90 μm.
[0059] 3) The modified polyetheretherketone obtained after the surface carbonization treatment is subjected to surface high-frequency heat treatment, with a current frequency of 60 KHz.
[0060] 4) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by using ion plating technology, and titanium metal is deposited on the surface of the carbide layer to form a titanium carbide modified layer; the thickness of the formed titanium carbide modified layer is 110 μm.
[0061] 5) In a gas protection atmosphere, the modified polyetheretherketone was subjected to stress relief annealing to eliminate the surface residual stress, and a polyetheretherketone material S8 with high biological activity was obtained. The parameters of the stress relief annealing treatment were: annealing temperature 310°C, heat preservation for 1 hour, and then cooling with the furnace. Example 9
[0062] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0063] 2) Electron beam surface heat treatment is used to treat the pretreated polyetheretherketone at high temperature, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer, thereby obtaining a polyetheretherketone material with high biological activity. The parameters of the electron beam surface heat treatment are: sweep voltage 40KV, current 15mA, vacuum degree 10 -2 Pa. The thickness of the formed carbonized layer was 40 μm.
[0064] 3) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by metal transfer plating, and chromium metal is deposited on the surface of the carbide layer to form a chromium carbide modified layer; the thickness of the formed chromium carbide modified layer is 55 μm.
[0065] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S9 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Example 10
[0066] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0067] 2) Electron beam surface heat treatment is used to treat the pretreated polyetheretherketone at high temperature, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer, thereby obtaining a polyetheretherketone material with high biological activity. The parameters of the electron beam surface heat treatment are: sweep voltage 40KV, current 15mA, vacuum degree 10 -2 Pa. The thickness of the formed carbonized layer was 50 μm.
[0068] 3) Plasma immersion ion implantation is used to perform surface deposition treatment on the surface of the modified polyetheretherketone, and iron metal is deposited on the surface of the carbide layer to form an iron carbide modified layer; the thickness of the formed iron carbide modified layer is 65 μm.
[0069] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S10 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Embodiment 11
[0070] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0071] 2) Electron beam surface heat treatment is used to treat the pretreated polyetheretherketone at high temperature, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer, thereby obtaining a polyetheretherketone material with high biological activity. The parameters of the electron beam surface heat treatment are: sweep voltage 40KV, current 15mA, vacuum degree 10 -2 Pa. The thickness of the formed carbonized layer was 90 μm.
[0072] 3) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by using a microwave-assisted coating method, and chromium metal is deposited on the surface of the carbide layer to form a chromium carbide modified layer; the thickness of the formed chromium carbide modified layer is 95 μm.
[0073] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S11 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 300°C, heat preservation for 1 hour, and then cooling with the furnace. Example 12
[0074] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0075] 2) Electron beam surface heat treatment is used to treat the pretreated polyetheretherketone at high temperature, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer, thereby obtaining a polyetheretherketone material with high biological activity. The parameters of the electron beam surface heat treatment are: sweep voltage 40KV, current 15mA, vacuum degree 10 -2 Pa. The thickness of the formed carbonized layer was 70 μm.
[0076] 3) The surface of the modified polyetheretherketone is subjected to surface deposition treatment by using a hybrid vacuum deposition technique, and zirconium metal is deposited on the surface of the carbide layer to form a zirconium carbide modified layer; the thickness of the formed zirconium carbide modified layer is 90 μm.
[0077] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S12 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 310°C, heat preservation for 1 hour, and then cooling with the furnace. Example 13
[0078] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0079] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.2mm, scanning speed 80mm / s, power 2w. The thickness of the porous structure carbonized layer formed is 20μm.
[0080] 3) A hydroxyapatite coating is sprayed on the surface of the carbonized layer using vacuum plasma spraying technology; the thickness of the hydroxyapatite is 5 μm.
[0081] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S13 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 310°C, heat preservation 0.5h, and then cooling with the furnace. Embodiment 14
[0082] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0083] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.2mm, scanning speed 80mm / s, power 2w. The thickness of the porous structure carbonized layer formed is 20μm.
[0084] 3) Spraying a zirconium oxide coating on the surface of the carbide layer by cold spraying; the thickness of the zirconium oxide coating is 10 μm.
[0085] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S14 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 310°C, heat preservation 0.5h, and then cooling with the furnace. Embodiment 15
[0086] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0087] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.2mm, scanning speed 80mm / s, power 2w. The thickness of the porous structure carbonized layer formed is 20μm.
[0088] 3) Spraying a titanium oxide coating on the surface of the carbide layer by magnetron sputtering; the thickness of the titanium oxide is 15 μm.
[0089] 4) In a gas protection atmosphere, the modified polyetheretherketone was subjected to stress relief annealing to eliminate the surface residual stress, and a polyetheretherketone material S15 with high biological activity was obtained. The parameters of the stress relief annealing treatment were: annealing temperature 310°C, heat preservation 0.5h, and then cooling with the furnace. Example 16
[0090] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0091] 2) The pretreated polyetheretherketone was subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone was carbonized to form a carbonized layer; the parameters of the plasma surface treatment were: discharge frequency 15kHz, voltage 2.0kV, gas flow 5slpm, action time 60s, distance 20mm. The thickness of the carbonized layer was 8μm.
[0092] 3) A polylactic acid coating was constructed on the surface of the carbonized layer by dip coating to obtain a polyetheretherketone material with high bioactivity. The thickness of the polylactic acid was 6 μm.
[0093] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S16 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 150°C, heat preservation 0.5h, and then cooling with the furnace. Embodiment 17
[0094] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0095] 2) The pretreated polyetheretherketone was subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone was carbonized to form a carbonized layer; the parameters of the plasma surface treatment were: discharge frequency 15kHz, voltage 2.0kV, gas flow 5slpm, action time 60s, distance 20mm. The thickness of the carbonized layer was 8μm.
[0096] 3) A chitosan coating was constructed on the surface of the carbonized layer by spin coating to obtain a polyetheretherketone material with high biological activity. The thickness of the chitosan was 6 μm.
[0097] 4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate the surface residual stress, thereby obtaining a polyetheretherketone material S17 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 150°C, heat preservation 0.5h, and then cooling with the furnace. Embodiment 18
[0098] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0099] 2) The pretreated polyetheretherketone was subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone was carbonized to form a carbonized layer; the parameters of the plasma surface treatment were: discharge frequency 15kHz, voltage 2.0kV, gas flow 5slpm, action time 60s, distance 20mm. The thickness of the carbonized layer was 8μm.
[0100] 3) A polycaprolactone coating was constructed on the surface of the carbonized layer by spin coating to obtain a polyetheretherketone material with high biological activity. The thickness of the polycaprolactone was 6 μm.
[0101] Step (4) In a gas protection atmosphere, the modified polyetheretherketone is subjected to stress relief annealing treatment to eliminate surface residual stress, thereby obtaining a polyetheretherketone material S18 with high biological activity. The parameters of the stress relief annealing treatment are: annealing temperature 150° C., heat preservation 0.5 h, and then cooling with the furnace. Comparative Example 1
[0102] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0103] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by electron beam surface heat treatment, so that the surface of the polyetheretherketone is carbonized, and the thickness of the formed carbonized layer is 10 μm.
[0104] 3) Under a gas protection atmosphere, the polyetheretherketone obtained in step (2) is directly subjected to stress relief annealing treatment to eliminate surface residual stress, thereby obtaining the final polyetheretherketone material D1. The parameters of the stress relief annealing treatment are: annealing temperature 300° C., heat preservation for 1 hour, and then cooling with the furnace. Comparative Example 2
[0105] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants; compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min.
[0106] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by plasma surface treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer with a thickness of 50μm. The parameters of the plasma surface treatment are: discharge frequency 15kHz, voltage 2.0kV, gas flow 5slpm, action time 60s, and distance 20mm.
[0107] 3) Under a gas protection atmosphere, the modified polyetheretherketone obtained in step (2) is subjected to stress relief annealing treatment to eliminate surface residual stress, thereby obtaining the final polyetheretherketone material D2. The parameters of the stress relief annealing treatment are: annealing temperature 150° C., heat preservation 0.5 h, and then cooling with the furnace. Comparative Example 3
[0108] 1) Use compressed air to pre-treat PEEK to remove surface burrs, dust and other contaminants. Compressed air parameters: treatment time: 1min, treatment temperature: room temperature, pressure: 12bar, flow rate: 100L / min.
[0109] 2) The pretreated polyetheretherketone is subjected to high temperature surface treatment by laser treatment, so that the surface of the polyetheretherketone is carbonized to form a carbonized layer; the parameters used for laser treatment are: scanning interval 0.1mm, scanning speed 60mm / s, power 2w. The thickness of the formed carbonized layer is 30μm.
[0110] 3) Under a gas protection atmosphere, the polyetheretherketone obtained in step (2) is subjected to stress relief annealing treatment to eliminate surface residual stress, thereby obtaining the final polyetheretherketone material D3. The parameters of the stress relief annealing treatment are: annealing temperature 250° C., heat preservation for 1 hour, and then cooling with the furnace. Comparative Example 4
[0111] 1) Use compressed air to pre-treat polyetheretherketone to remove burrs, dust and other pollutants on its surface. Obtain polyetheretherketone material D0. Compressed air parameters: treatment time: 1 min, treatment temperature: room temperature, pressure: 12 bar, flow rate: 100 L / min. Experimental Example 1: Biocompatibility Experiment
[0112] The surface of the modified polyetheretherketone material prepared in Examples 1-18 and Comparative Examples 1-4 was ultrasonically cleaned with deionized water and dried. The dried samples were used to detect cell proliferation and viability through CCK-8 test. Mouse osteoblasts (MC3T3-E1 cells) were cultured at 2 x 10 4 The cells were inoculated at a density of 100 cells / well in a 24-well plate, each well containing 2 ml of culture medium, and placed in an incubator at 37°C and 5% carbon dioxide. After co-culture with polyetheretherketone materials for a certain period of time, the proliferation and viability of the cells were evaluated according to the instructions of the kit. The CCK-8 test results were measured at 450nm, and the quantitative absorption peaks were compared in the form of data. The results are shown in Figure 1 shown.
[0113] Cell survival rate (%) = OD value of sample group / OD value of blank control group × 100%.
[0114] Group Cell survival rate (%) Example 1 109.59 Example 2 118.30 Example 3 115.61 Example 4 120.84 Example 5 113.37 Example 6 117.22 Example 7 109.30 Example 8 116.48 Example 9 114.40 Example 10 122.12 Embodiment 11 122.54 Example 12 119.84 Example 13 126.94 Embodiment 14 112.91 Embodiment 15 120.51 Example 16 127.02 Embodiment 17 135.12 Embodiment 18 128.77 Comparative Example 1 100.08 Comparative Example 2 98.42 Comparative Example 3 101.37 Comparative Example 4 92.53 The embodiments of the present invention are described in detail above, but the contents described are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.
Claims
1. A method for preparing a polyetheretherketone material, characterized in that: The steps include: 1) Pre-treat PEEK, clean the surface and remove surface burrs; 2) performing high-temperature carbonization treatment on the surface of the pretreated polyetheretherketone to carbonize the surface of the polyetheretherketone to form a porous carbonized layer with a porous structure; 3) performing surface deposition treatment on the modified polyetheretherketone obtained in step 2), directly depositing a carbide coating on the surface of the porous structure carbonized layer, or depositing a metal coating, a bioceramic coating or a polymer coating on the surface of the porous structure carbonized layer; 4) Post-treating the modified polyetheretherketone obtained in step 3) to eliminate surface residual stress, thereby obtaining a polyetheretherketone material with high biological activity.
2. The method for preparing a polyetheretherketone material according to claim 1, characterized in that: The porous carbonized layer in step 2) has a thickness of 5-100 μm, a porosity of 20-80%, a pore size of 20-50 μm, and a specific surface area of 1.5-4.5 m 2 / g.
3. The method for preparing a polyetheretherketone material according to claim 2, characterized in that: In step 2), the surface is carbonized and then subjected to high-frequency heat treatment.
4. The method for preparing a polyetheretherketone material according to claim 3, characterized in that: The post-treatment in step 4) includes stress relief annealing and tempering.
5. A method for preparing a polyetheretherketone material according to any one of claims 1 to 4, characterized in that: The process of directly depositing the carbide coating on the surface of the porous carbonized layer in step 3) includes: cold spraying, chemical vapor deposition or electrophoretic deposition.
6. A method for preparing a polyetheretherketone material according to any one of claims 1 to 4, characterized in that: In the step 3), a metal coating is deposited on the surface of the porous structure carbonized layer, and the metal reacts with the surface carbonized layer to form a carbide modified layer. The process of depositing metal on the surface of the carbonized layer includes: DC magnetron sputtering, pulsed laser deposition, ion plating, chemical vapor deposition, cold spraying, metal transfer plating, plasma immersion ion implantation, microwave assisted coating or mixed vacuum deposition.
7. A method for preparing a polyetheretherketone material according to any one of claims 1 to 4, characterized in that: The carbide directly deposited in step 3) or the carbide generated by reacting with the metal after the metal is deposited includes titanium carbide, zirconium carbide, tantalum carbide, niobium carbide, tungsten carbide, molybdenum carbide, chromium carbide, manganese carbide, iron carbide, magnesium carbide or silicon carbide.
8. A method for preparing a polyetheretherketone material according to any one of claims 1 to 4, characterized in that: The process of depositing a bioceramic coating on the surface of the carbonized layer in step (3) includes: cold spraying, magnetron sputtering or vacuum plasma spraying, and the bioceramic includes: bioglass, zirconium oxide, titanium oxide, calcium phosphate or calcium silicate, and the thickness of the overall carbide modified layer is 10-120 μm.
9. A method for preparing a polyetheretherketone material according to any one of claims 1 to 4, characterized in that: The process for constructing the polymer coating on the surface of the carbonized layer is dip coating, spin coating or vacuum spraying. The polymer material in step (3) includes polylactic acid, polycaprolactone or chitosan. The thickness of the overall carbide modified layer is 10-120 μm.
10. A polyetheretherketone material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.