Laminate design carbon fiber reinforced ppesk medical composite and preparation method thereof

By using PPESK resin and a specific layup design, the problem of modulus mismatch in carbon fiber composite materials has been solved, achieving low elastic modulus and high strength that match human bone, thus meeting the biocompatibility and mechanical requirements of orthopedic implants.

CN122097682APending Publication Date: 2026-05-29DALIAN UNIV OF TECH

Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
DALIAN UNIV OF TECH
Filing Date
2026-04-16
Publication Date
2026-05-29

AI Technical Summary

Technical Problem

The flexural modulus of existing carbon fiber reinforced composites far exceeds that of human cortical bone, resulting in a stress shielding effect. Furthermore, traditional methods have failed to achieve an effective match between biocompatibility and interfacial bonding strength.

Method used

A carbon fiber reinforced PPESK medical composite material with a flexural modulus close to that of cortical bone was prepared by using diazanaphthone biphenyl ether sulfone ketone (PPESK) resin combined with solution impregnation method and specific layup design. Through the quasi-isotropic layup structure of [90°/±45°/0°]s, the modulus was reduced to 32GPa while maintaining high strength.

Benefits of technology

It achieves a low elastic modulus that matches human bone structure, eliminates stress shielding effect, and possesses excellent biocompatibility and interfacial bonding strength, meeting the mechanical requirements of orthopedic implants.

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Abstract

The application discloses a kind of carbon fiber reinforced PPESK medical composite of layer design and preparation method thereof, the present application is impregnated by 10%-20% mass fraction of PPESK / NMP solution using desizing carbon fiber, multi-section gradient temperature drying and water washing or organic solvent purification, obtain low-impurity prepreg tape;Through quasi-isotropic [90° / ±45° / 0°] s layer design, the product obtained by combining 16MPa, 360 ℃ vacuum hot pressing molding realizes the matching with human bone mechanical property, and the bending modulus is adjusted from 143GPa to 32GPa, the bending strength reaches 489MPa, and the interlaminar shear strength is 44.2MPa.The beneficial effects of the present application are that the mechanical properties are precisely controlled through the layer structure, high strength, low modulus and high biological safety are considered, the process is stable and controllable, suitable for orthopedic load-bearing bone implant material, to provide high-performance, high-adaptability new composite material solution for bone implant device.
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Description

Technical Field

[0001] This invention belongs to the field of biomedical materials technology, specifically relating to a carbon fiber reinforced PPESK medical composite material based on layup design and its preparation method. Background Technology

[0002] In the field of orthopedic implants, traditional metallic materials (such as stainless steel, cobalt-chromium alloys, and titanium alloys) are prone to stress shielding after implantation due to their excessive rigidity. This effect reduces the mechanical stimulation received by the host bone, leading to bone resorption and implant loosening. In recent years, carbon fiber reinforced polyetheretherketone (CF / PEEK) has become a revolutionary material for orthopedic implants due to its excellent mechanical strength, biocompatibility, and radiolucency. However, the flexural modulus of traditional unidirectional (UD) carbon fiber reinforced thermoplastic composites typically exceeds 120 GPa, far exceeding the modulus of human cortical bone (15-25 GPa), and the problem of mechanical property mismatch still exists. If relying solely on unreinforced resin matrices, their strength is insufficient to meet the surgical requirements of load-bearing implants. Therefore, it is necessary to develop a new composite material that possesses sufficient strength and a low elastic modulus that matches human bone to eliminate stress shielding and meet the needs of medical devices.

[0003] In existing technologies, CN117283899A proposes a method for designing the elastic modulus of quasi-isotropic composite materials. This method involves adjusting the modulus through balanced and symmetrical layering of unidirectional fiber strips, fabrics, and felts. However, it only uses a combination of general-purpose fibers and a matrix, failing to precisely adjust the modulus to the cortical bone region for bone implantation applications, resulting in insufficient biocompatibility and interfacial bonding strength. Therefore, developing carbon fiber-reinforced thermoplastic medical composite materials with sufficient strength, bone-matched low elastic modulus, and excellent biocompatibility has become a pressing technical problem in the field of orthopedic implant materials. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a carbon fiber reinforced PPESK medical composite material based on a layup design and its preparation method. Using diazanaphthone biphenyl ether sulfone ketone (PPESK) resin, combined with a solution impregnation method and a specific layup design, a medical composite material with both high strength and bone-matching modulus is prepared. This achieves a flexural modulus reduced to 32 GPa (close to cortical bone's 15–25 GPa) while maintaining a flexural strength of 485 MPa, eliminating stress shielding and meeting orthopedic implant mechanical standards.

[0005] The technical solution of the present invention is as follows: A method for preparing a layered carbon fiber reinforced PPESK medical composite material, comprising the following steps: Step 1: Prepreg preparation: The carbon fiber bundles after removing the sizing agent are immersed in a PPESK / NMP solution with a mass fraction of 10%-20% and dried through multi-stage gradient heating to obtain CF / PPESK prepreg. Step 2: The pre-impregnated tape is washed and purified with water or organic solvent, and then dried; Step 3: Lay-up and stack the prepreg tapes at a preset angle to form the shape; Step 4: Hot pressing molding. The prepreg tape after layup is placed in a mold, and vacuum degassing, pressure holding, and cooling are performed under set pressure and temperature to obtain carbon fiber reinforced PPESK medical composite material.

[0006] Preferably, the desizing treatment of carbon fiber in step 1 involves refluxing in acetone for 3 days to remove the commercial sizing agent.

[0007] Preferably, the immersion time in step 1 is 3 minutes; the multi-stage gradient temperature rise is 150℃, 180℃, 210℃, 240℃ and 280℃ respectively, to fully evaporate the solvent NMP.

[0008] Preferably, the water washing and purification conditions are: water temperature 80℃-100℃, water washing time 4h-8h, stirring speed 400rpm-800rpm, and the mass-volume ratio of pre-soaked tape to water is 1g:400ml-1g:600ml.

[0009] Preferably, the organic solvent is a poor solvent for PPESK and is miscible with NMP.

[0010] Preferably, the pre-impregnation tape water washing purification includes fixing the CF / PPESK in a glass container, adding sufficient deionized water until it covers the pre-impregnation tape, and performing water washing purification under magnetic stirring conditions.

[0011] Purification significantly reduces both NMP and heavy metal ion content, minimizing the threat to health posed by residual solvents and the leaching of heavy metal ions.

[0012] Preferably, the layup structure in step 2 is a quasi-isotropic structure [90° / ±45° / 0°]s, or selected from unidirectional structures [0°]s and orthogonal structures [0° / 90°]s.

[0013] Preferably, in step 3, the molding pressure is 16 MPa, the hot pressing temperature is 360°C, the high-temperature holding time is 40 minutes, and the vacuum degree is ≤-0.09 MPa.

[0014] A layered carbon fiber reinforced PPESK medical composite material is prepared by the method described above.

[0015] The material has a flexural modulus ranging from 32 GPa to 143 GPa and a flexural strength ranging from 482.4 MPa to 1537.2 MPa.

[0016] Preferably, the flexural modulus is 32 GPa-60 GPa and the flexural strength is 482.4 MPa-825 MPa; furthermore, when the flexural modulus is 32 GPa, it matches the 15-25 GPa of human cortical bone.

[0017] Preferably, the interlaminar shear strength is 44.2 MPa-82.7 MPa. The quasi-isotropic layup structure gives the composite material excellent impact resistance, with no delamination failure under low-speed impact. The impact resistance from high to low is quasi-isotropic structure > orthogonal structure > unidirectional structure.

[0018] Preferably, the relative survival rate of MC3T3-E1 pre-osteoblasts is consistently higher than 80%, with no significant cytotoxicity, meeting the biocompatibility requirements of orthopedic implant materials.

[0019] Preferably, the application of composite materials in the preparation of orthopedic load-bearing bone implants, wherein the orthopedic load-bearing bone implants can effectively eliminate stress shielding effects and meet the ASTM F382 bone plate mechanical standard.

[0020] The beneficial effects of this invention are: 1. Good mechanical compatibility and elimination of stress shielding: The QI layup structure of [90° / ±45° / 0°]s is adopted, which reduces the flexural modulus of the composite material to 32GPa, which is very close to that of human cortical bone (15-25GPa), while retaining a flexural strength of 489MPa, thus achieving a balance between stiffness and strength.

[0021] 2. Strong interfacial bonding: Thanks to the excellent solubility of PPESK in organic solvents, the solution impregnation method allows resin solutions with a mass fraction of 10%-20% to fully wet the carbon fibers, significantly improving the integrity of the resin-fiber interface and the overall mechanical properties of the material.

[0022] 3. Excellent impact resistance: Due to its multi-angle fiber distribution, the QI ply structure can effectively redistribute the load and suppress the initiation and propagation of cracks. No delamination failure occurred in the low-speed impact test, demonstrating the best impact resistance.

[0023] 4. Optimization of water washing for material application in medical implants: Prepreg tapes prepared with resin solutions in the range of 10%-20% by mass are significantly reduced in organic solvent and heavy metal ion content after water washing and purification, meeting the high purity requirements of medical bone implant materials.

[0024] 5. Excellent biocompatibility: In in vitro cell experiments, the relative survival rate of the material extract against MC3T3-E1 pre-osteoblasts was consistently above 80%, with good cell adhesion and spreading, and no obvious cytotoxicity, demonstrating excellent potential for application in orthopedic medical devices. Attached Figure Description

[0025] Figure 1 The results are the test results of heavy metal ion content in the prepreg tape in Example 1.

[0026] Figure 2 The NMP content test results are for the prepreg tape in Example 1.

[0027] Figure 3 The diagram below shows the preparation process and layup structure of the CF / PPESK composite material in Example 2.

[0028] Figure 4 The results of the three-point bending performance test and the stress-strain curve of the composite material in Example 2 are shown.

[0029] Figure 5 The results are the interlaminar shear strength (SBS) test results of the composite material in Example 2.

[0030] Figure 6 The results are the tensile properties test results of the composite material in Example 2.

[0031] Figure 7 The dynamic thermomechanical analysis (DMA) curves (storage modulus and loss factor) of the composite material in Example 2 are shown.

[0032] Figure 8 The figures show the contact force-time and maximum contact force-energy curves for different ply structures under low-speed impact in Example 2.

[0033] Figure 9 The image shows an ultrasonic non-destructive testing (D-scan) image of the laminate after the impact test in Example 2.

[0034] Figure 10 This is a scanning electron microscope (SEM) image of the bending fracture surface of the composite material in Example 2.

[0035] Figure 11 The results show the relative cell viability test results of MC3T3-E1 cells co-cultured for 1 day and 3 days in Example 3.

[0036] Figure 12 This is the result of MC3T3-E1 cells adhering to the surface of the composite material in Example 3.

[0037] Figure 13 The results are the test results of heavy metal ion content in the prepreg tape in Example 4.

[0038] Figure 14 The NMP content test results are for the prepreg tape in Example 4.

[0039] Figure 15The results are the test results of heavy metal ion content in the prepreg tape in Example 5.

[0040] Figure 16 The NMP content test results are for the prepreg tape in Example 5. Detailed Implementation

[0041] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0042] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. 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.

[0043] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0044] The present invention will be further described below with reference to specific embodiments. The scope of the present invention is not limited to the following embodiments and can be adjusted according to actual circumstances.

[0045] The physical properties of the prepreg tape were characterized according to GB / T3855-2005 and HB 7736 standards. The three-point bending, interlaminar shear, and tensile properties of the composite material were measured using an Instron 5567A universal testing machine, and the low-velocity impact behavior was characterized using a 9250HV drop hammer oscilloscope impact tester. The heavy metal ion content of the prepreg tape was analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES), and the NMP content was analyzed using liquid chromatography-mass spectrometry (LC-MS). The bending cross-sectional morphology of the composite material was analyzed using scanning electron microscopy (SEM). Damage analysis of the samples after the drop hammer impact test was performed using phased array ultrasonic nondestructive testing.

[0046] The three-point bending test of the composite material was conducted as follows: The flexural properties of the CF / PPESK composite material were tested according to the three-point bending method in ASTM D790 standard. Composite material specimens with different layup structures and dimensions of 80 × 12.5 × 2 mm were used. The testing instrument was an Instron 5567A universal testing machine, with a span L = 64 mm, a loading head radius R = 5 mm, and a loading rate of 1 mm / min. Five parallel tests were performed for each sample, and the results were taken as the arithmetic mean.

[0047] The interlaminar shear test of the composite material was conducted as follows: According to ASTM D2344, the short beam shear (SBS) test was used to evaluate the interfacial bond strength between the resin and carbon fiber. Five shear specimens measuring 12 mm × 4 mm × 2 mm were used per group. The test platform was an Instron 5567A universal testing machine with a span L = 8 mm, a loading head radius R = 3 mm, and a loading rate of 1 mm / min. The arithmetic mean of the maximum loads was taken, and the interlaminar shear strength (ILSS) of the composite material was calculated using Formula 2.5.

[0048] F – The maximum load the sample can withstand, in N. b – Sample width, in mm h – Sample thickness, in mm The tensile properties of the composite material were tested as follows: According to ASTM D3039, a suitable tensile reinforcing sheet was selected. The reinforcing sheet protects the specimen from damage by the clamps and distributes the clamping force evenly to the test area, preventing premature failure of the specimen at the clamping point. In this experiment, an aluminum alloy sheet with dimensions of 56mm × 15mm × 1mm and a 90° bevel angle was selected. First, the surface of the specimen and the reinforcing sheet was sanded with coarse sandpaper to remove release agent residue and increase the surface area. Adhesive was then evenly applied to the treated surface. The reinforcing sheet was then attached to the tensile specimen surface and appropriate pressure was applied to allow the adhesive to cure. The CF / PPESK composite material with the reinforcing sheet attached was cut into 250mm × 15mm × 1mm pieces for tensile testing. The prepared standard specimen is vertically fixed on the fixture of the universal testing machine, ensuring that the tensile axis coincides with the center of the specimen. The testing machine applies axial tensile force at a constant speed of 1 mm / min, causing the specimen to continuously deform under stress until it finally breaks. The system records the tensile force value and deformation in real time, and converts them into stress-strain curves through calculation, thereby obtaining the tensile strength, elastic modulus and elongation at break of the material.

[0049] The low-velocity impact test of composite materials was conducted as follows: To verify the impact resistance characteristics of CF / PPESK laminates with different ply structures, this study used the Instron 9250HV drop hammer impact testing platform for experimental testing. During the experiment, load and displacement sensors were used to collect and record the characteristic curves of impact force versus time and displacement in real time. The test strictly followed the ASTM D7136M-15 standard, using a 16 mm diameter, 4.11 kg steel hemispherical punch. A laminate sample with dimensions of 150 mm × 100 mm × 4.8 mm was fixed in a ring clamp with an inner diameter of 60 mm to ensure that the impact point was accurately applied to the center of the sample. The ply structures of the samples were unidirectional, orthogonal, and quasi-isotropic, with impact energies of 6 J, 9 J, and 12 J, respectively.

[0050] Example 1: Preparation and parameter optimization of prepreg tape.

[0051] The carbon fiber (Torayca T700-SC) was refluxed in acetone for 3 days to remove the sizing agent. PPESK / NMP solutions with mass fractions of 10%, 15%, and 20% were prepared. The desized carbon fiber was immersed in approximately 500 mL of the resin solution for 3 minutes, followed by drying in a programmed temperature oven (multi-stage temperature gradient increases at 150°C, 180°C, 210°C, 240°C, and 280°C to fully evaporate the NMP solvent). The physical properties of the prepreg tape are shown in Table 1. Tests show that the physical properties of prepreg tapes prepared within the resin solution mass fraction range of 10% to 20% all meet the requirements. In particular, the prepreg tape prepared with a 15wt% solution has a resin mass fraction of 33.88%, a porosity of only 1.43%, no microcracks on the surface, and no obvious resin-rich areas, exhibiting excellent performance. Its thickness is 0.125 mm. The prepreg tape prepared with the 15wt% solution was washed with water at 100℃ for 4-8 hours, with a stirring speed of 600 rpm and a prepreg tape to water mass-to-volume ratio of 1 g:500 ml. Figure 1 and Figure 2 The impurity content test results showed that the content of organic solvent NMP and heavy metal ions in the prepreg belt decreased significantly after water washing.

[0052] Table 1 Physical properties of different prepreg tapes Solution concentration (%) Resin mass fraction (%) <![CDATA[Areal density of prepreg tape (g / m 2 )]]> Porosity (%) Fiber volume content (%) 10 18.81 133.6 2.24 74.4 15 33.88 146.1 1.43 58.1 20 39.44 164.9 1.38 52.3 Example 2: Preparation and mechanical property evaluation of laminates with different layup structures.

[0053] The prepreg tapes prepared from the 15wt% solution in Example 1 were processed according to unidirectional (UD: [0°) 16s Orthogonal (CP: [0° / 90°]) 8s ) and quasi-isotropic (QI: [90° / ±45° / 0°]) 4sand [0° / 90° / ±45°] 4s The deployment will be carried out according to the following scheme, such as Figure 3 As shown in the figure. The composite material was hot-pressed at 16 MPa pressure and 360℃ for 40 minutes. The mechanical properties of the composite material prepared by the above method are as follows: The results of the three-point bending test are as follows: Figure 4 As shown, the flexural strength and modulus of the UD ply are 1537.2 MPa and 143 GPa, respectively, while the flexural strength and modulus of the CP ply are 482.4 MPa and 60 GPa, respectively; the QI-1 ply ([0° / 90° / ±45°]) 4s The flexural strength and modulus of QI-2 are 825 MPa and 57.8 GPa, respectively, while the flexural strength and modulus of QI-2 ([90° / ±45° / 0°]) are 57.8 GPa. 4s The values ​​are 489 MPa and 32 GPa. In comparison, the QI-2 layup design enables the composite material to achieve a modulus of 32 GPa (avoiding stress shielding effect) and a strength of 489 MPa (meeting the ASTM F382 bone plate standard), achieving bone-matched mechanical properties.

[0054] Interlaminar shear test results are as follows Figure 5 As shown, the interlaminar shear strengths (ILSS) of CF / PPESK@UD, CF / PPESK@CP, and CF / PPESK@QI are 82.7 MPa, 47 MPa, and 44.2 MPa, respectively, showing a clear decreasing trend. This phenomenon is attributed to the combined effect of internal residual thermal stress and stress concentration during hot pressing. Comprehensive analysis shows that the QI layup laminate has the lowest interlaminar shear strength, while the CP layup has a relatively higher one. The UD layup exhibits the best shear performance due to the tight adhesion between the layers.

[0055] Tensile property test results as follows Figure 6 As shown, the tensile strength and elastic modulus of CF / PPESK@UD, CF / PPESK@CP, and CF / PPESK@QI are 1707 MPa, 751 MPa, and 535 MPa, and 156 GPa, 85 GPa, and 61 GPa, respectively. Analysis indicates that the tensile properties of the composite materials are entirely dominated by the fibers arranged along the tensile direction.

[0056] Dynamic thermomechanical test results as follows Figure 7 As shown, when 0° layup (fiber direction aligned with the load) dominates, the material exhibits the highest stiffness and storage modulus in the direction of stress, due to the maximum axial stiffness of the fibers. Multi-angle layups (QI) (±45°, 90°) reduce the overall storage modulus because diagonal or transverse layups contribute less to axial stiffness. CP layup ([0° / 90°]) sThis results in a modulus between that of unidirectional layups and pure matrix, forming an anisotropic but balanced stiffness distribution. The peak values ​​of Tanδ are QI > CP > UD. This is because in the QI ([0 / 90 / ±45]s) structure, the multi-angle layups increase the degree of interlaminar shear and matrix deformation, leading to enhanced energy dissipation and a significantly higher loss factor. The loss factor of the 0°-dominated layup is lower because the resin deformation is smaller when the fiber dominates the load. Orthogonal layups have large-angle layup differences, which intensifies the interfacial shear stress, promotes interlaminar friction and resin plastic deformation, and significantly increases the loss factor.

[0057] The results of the low-velocity impact test are as follows Figure 8 As shown, normal impact has a similar effect on fibers arranged in all directions within the composite material; however, the different fiber orientations within the composite material can influence crack propagation. Figure 8 It can be seen that the maximum contact force of orthogonal ply laminates, regardless of whether the impact energy is 6J, 9J, or 12J, is higher than that of UD ply materials. Comparing the maximum contact forces of CP and QI ply laminates under the same impact energy, the values ​​for QI ply are consistently higher than those for CP. Combined with... Figure 8 (b) It can be concluded that under the same conditions, the impact resistance of the three types of CF / PPESK laminates is QI > CP > UD.

[0058] Ultrasonic nondestructive testing results are as follows Figure 9 As shown, in summary, the ultrasonic D-scan results combined with previous low-velocity impact test results indicate that the QI layup laminate exhibits superior impact resistance compared to CP and UD, with CP also outperforming UD. Analyzing the failure mechanism, this is because the laminate suffers internal damage such as delamination and fracture during impact. The distribution of fibers with different orientations can, to some extent, disperse stress transmission and inhibit crack propagation. The damage formed by the QI layup laminate under impact is essentially the same as that of the CP layup laminate; however, because the fibers arranged in the ±45° direction inhibit crack initiation and propagation, this layup structure has better impact resistance.

[0059] The cross-sectional morphology of the composite material after mechanical property testing (flexural strength) is as follows: Figure 10 As shown, the flexural fracture failure modes of composite materials with different ply structures after flexural testing can be analyzed intuitively. From Figure 10 (a) and (d) show that the CF / PPESK@UD laminate experienced brittle fracture of the fibers, with a relatively smooth fracture surface, indicating sample failure; the CF / PPESK@CP laminate showed severe delamination between the 0° and 90° layers, which ultimately led to tensile fracture at the 0° layup. Figure 10As shown in (c) and (f), Type I open-end interlaminar failure occurs over a large area in the CF / PPESK@QI laminate. The greater the layup angle misalignment, the larger the area of ​​interlaminar failure. Specifically, the interlaminar failure manifests as fiber debonding. This is because the interlaminar bonding force of the QI laminate is weak. Under external loads, the matrix resin has a weak load-bearing capacity and is prone to cracking within the resin matrix. As the load increases, the cracks propagate, causing matrix cracking within a small area, separation from the fiber phase, and fiber debonding, leading to premature sample failure.

[0060] Example 3: Biocompatibility Testing. The MTT assay was used to assess the cytotoxicity of the materials. Since both cytotoxicity and cell adhesion experiments were performed on the material surface, the surface layers of the three composite materials with different layup structures were all 0° oriented. A representative unidirectional layup sample from the materials prepared in the 15 wt% solution in Example 2 was immersed in MEM-α medium to prepare an extract. MC3T3-E1 cells were cultured in extracts of different concentrations for 1 and 3 days. The results are as follows: Figure 11 As shown, the cell survival rate in all test groups exceeded 80%, and the metabolic activity after 3 days of culture was generally higher than that after 1 day, proving that the composite material does not interfere with normal cell proliferation and has no obvious cytotoxicity. Images of cell adhesion on the material surface observed by confocal microscopy are shown below. Figure 12 As shown, the cells exhibit spherical nuclei and obvious pseudopodia extensions on the material surface, and are evenly distributed, confirming that the material surface can effectively support cell adhesion and growth.

[0061] Example 4: The water washing method is the same as in Example 1, but the washing time is 4 hours, and the washing temperature is 80℃, 90℃, or 100℃. Figure 13 and 14 As shown, the content of heavy metal ions in the prepreg belt was significantly reduced after water washing, with some reaching the detection limit, and the NMP content also decreased significantly.

[0062] Example 5: The water washing method is the same as in Example 1, but the washing time is 4 hours, and the stirring speed is 400 rpm, 600 rpm, and 800 rpm. Figure 15 and 16 As shown, the content of heavy metal ions in the prepreg belt was significantly reduced after water washing, with some reaching the detection limit, and the NMP content also decreased significantly.

Claims

1. A method for preparing a layered carbon fiber reinforced PPESK medical composite material, characterized in that, Includes the following steps: Step 1: Prepreg preparation: The carbon fiber bundles after removing the sizing agent are immersed in a PPESK / NMP solution with a mass fraction range of 10%-20%, and dried by multi-stage gradient heating to obtain CF / PPESK prepreg tape, which is then washed and purified with water or organic solvent and dried. Step 2: Lay-up and stack the prepreg tapes at a preset angle to form the shape; Step 3: Hot pressing molding. The prepreg tape after layup is placed in a mold, and vacuum degassing, pressure holding, and cooling are performed under set pressure and temperature to obtain carbon fiber reinforced PPESK medical composite material.

2. The preparation method according to claim 1, characterized in that, In step 1, the carbon fiber desizing process involves refluxing in acetone for 3 days to remove the commercial sizing agent.

3. The preparation method according to claim 1, characterized in that, The immersion time in step 1 is 3 minutes; the multi-stage gradient temperature rise is 150℃, 180℃, 210℃, 240℃ and 280℃ respectively, to fully evaporate the solvent NMP.

4. The preparation method according to claim 1, characterized in that, In step 1, the water washing and purification conditions are 80℃-100℃, the water washing time is 4h-8h, the stirring speed is 400rpm-800rpm, and the mass-volume ratio of the pre-soaked tape to water is 1g:400ml-1g:600ml.

5. The preparation method according to claim 1, characterized in that, In step 2, the layup structure adopts a quasi-isotropic structure [90° / ±45° / 0°]s, or is selected from a unidirectional structure [0°]s or an orthogonal structure [0° / 90°]s.

6. The preparation method according to claim 1, characterized in that, In step 3, the molding pressure is 16 MPa, the hot pressing temperature is 360℃, the high-temperature holding time is 40 minutes, and the vacuum degree is ≤-0.09 MPa.

7. A layered carbon fiber reinforced PPESK medical composite material, characterized in that, Prepared by the method described in any one of claims 1-6.

8. The composite material according to claim 7, characterized in that, The flexural modulus ranges from 32 GPa to 143 GPa, the flexural strength ranges from 482.4 MPa to 1537.2 MPa, and the interlaminar shear strength ranges from 44.2 MPa to 82.7 MPa.

9. The composite material according to claim 7, characterized in that, The relative survival rate of MC3T3-E1 pre-osteoblasts remained above 80%.

10. The application of the composite material of claim 7 in the preparation of orthopedic load-bearing bone implant materials.