Novel Carbon Fiber Reinforced Surface Porous Composite Material and Preparation Method Thereof

Abstract

The present application discloses a novel carbon fiber-reinforced surface porous composite material and a preparation method thereof, belonging to the field of material technology, including: two functionalized porous structures, a plurality of carbon fiber polyether ether ketone prepregs and a plurality of polyether ether ketone films, and each carbon fiber polyether ether ketone prepreg and each polyether ether ketone film are alternately laid between the two functionalized porous structures according to a preset laying sequence; the functionalized porous structure is a hot-pressed polyether ether ketone mixture, and the carbon fiber polyether ether ketone prepreg is a first carbon fiber polyether ether ketone prepreg with a laying direction of 0° or a second carbon fiber polyether ether ketone prepreg with a laying direction of 90°. The carbon fiber-reinforced surface porous composite material provided by the present application can adjust the relative thickness of each layer and the laying sequence of the carbon fiber polyether ether ketone prepreg and the polyether ether ketone film to match different mechanical properties, and is suitable for fields such as artificial bone repair, catalysts, adsorbents, insulating materials, and electromagnetic shielding.

Description

Technical Field

[0001] The present application relates to a novel carbon fiber reinforced surface porous composite material and a preparation method thereof, belonging to the field of material technology. Background Art

[0002] Polyetheretherketone (PEEK) has many advantages, such as excellent mechanical properties, electrical properties, wear resistance, heat resistance, chemical resistance, good biocompatibility, elastic modulus close to that of human bone, radiopacity, easy processing, and repeatable disinfection. These advantages make it of great significance in the application research in various fields and become one of the candidate materials to replace stainless steel, titanium alloy, ultra-high molecular weight polyethylene, etc. However, due to its stable chemical structure and relatively low surface energy, PEEK has a relatively hydrophobic surface, which makes its functions such as bone integration and bioactivity poor. Therefore, in the prior art, PEEK is usually made into a surface porous structure, but the use of a porous structure will greatly reduce its mechanical properties.

[0003] Taking orthopedic implants as an example, since a single-structured PEEK is difficult to complete the rapid response of cells, regulate the directional differentiation of stem cells, and ensure angiogenesis and nutrient transport during the tissue regeneration process, researchers have made PEEK repair systems into a multi-level micro-nano pore structure to construct a polyetheretherketone implant with a rapid repair function. Among them, the micron-level connected network structure will ensure the smooth growth of tissues and nutrient delivery, and the nano-pore structure promotes the adhesion and differentiation of in vivo cells through the controlled release of growth factors. At the same time, a degradable bioactive material can be filled in the voids of the material. After this multi-level structured material is implanted into the human body, tissues will grow into the voids of the material, thereby improving the bonding strength between the material and human tissues. Hydroxyapatite (HA) is the main inorganic component of human and animal bones. It can achieve chemical bond combination with the body tissue at the interface, has a certain solubility in the body, can release ions harmless to the body and participate in the body metabolism, has a stimulating or inducing effect on bone hyperplasia, can promote the repair of defective tissues, and shows bioactivity. However, while these bioactive ceramics improve the bioactivity of PEEK, they reduce the excellent mechanical properties. Summary of the Invention

[0004] The purpose of the present application is to provide a novel carbon fiber reinforced surface porous composite material and a preparation method thereof. This surface porous composite material improves the functions of PEEK such as bioactivity while also having excellent mechanical properties, and the mechanical properties are designable.

[0005] To achieve the above purpose, the first aspect of the present application provides a novel carbon fiber reinforced surface porous composite material, including:

[0006] Two functionalized porous structures, a number of carbon fiber polyether ether ketone prepregs, and a number of polyether ether ketone films, with each carbon fiber polyether ether ketone prepreg and each polyether ether ketone film alternately laid between the two functionalized porous structures according to a preset layering sequence;

[0007] The functionalized porous structure is a polyether ether ketone mixture after hot pressing. The carbon fiber polyether ether ketone prepreg is a first carbon fiber polyether ether ketone prepreg with a laying direction of 0° or a second carbon fiber polyether ether ketone prepreg with a laying direction of 90°.

[0008] In one embodiment, the surface porous composite material includes 4 layers of polyether ether ketone films and 7 layers of carbon fiber polyether ether ketone prepregs;

[0009] The preset layering sequence of the 4 layers of polyether ether ketone films and 7 layers of carbon fiber polyether ether ketone prepregs is as follows: polyether ether ketone film, first carbon fiber polyether ether ketone prepreg, second carbon fiber polyether ether ketone prepreg, polyether ether ketone film, first carbon fiber polyether ether ketone prepreg, second carbon fiber polyether ether ketone prepreg, first carbon fiber polyether ether ketone prepreg, polyether ether ketone film, second carbon fiber polyether ether ketone prepreg, first carbon fiber polyether ether ketone prepreg, polyether ether ketone film.

[0010] In one embodiment, the pore diameter of the functionalized porous structure is 0.6 mm, the thickness of the carbon fiber polyether ether ketone prepreg is 0.155 mm, and the thickness of the polyether ether ketone film is 0.157 mm.

[0011] In one embodiment, the polyether ether ketone mixture includes: polyether ether ketone and a bioactive material. Among them, the bioactive material is any one of hydroxyapatite, calcium phosphate ceramics, bioactive glass, zirconia, silicon nitride, and aluminate ceramics.

[0012] In one embodiment, the polyether ether ketone mixture includes: polyether ether ketone and a catalyst material. Among them, the catalyst material is any one of alumina, aluminosilicate, copper catalyst, molybdenum catalyst, and platinum group metal catalyst.

[0013] In one embodiment, the polyether ether ketone mixture includes: polyether ether ketone and an adsorbent material. Among them, the adsorbent material is any one of activated carbon, zeolite, activated alumina, and titanium oxide.

[0014] In one embodiment, the polyether ether ketone mixture includes: polyether ether ketone and an insulating material. Among them, the insulating material is any one of ceramic materials, silicone rubber, glass fiber, ceramic fiber, and silicone glue.

[0015] In one embodiment, the polyetheretherketone mixture comprises: polyetheretherketone and an electromagnetic shielding material, wherein the electromagnetic shielding material is any one of a copper alloy, a nickel-based alloy, a conductive ceramic material, a conductive coating material, and carbon fiber.

[0016] The second aspect of the present application provides a preparation method for preparing the novel carbon fiber-reinforced surface porous composite material as described in any one of the embodiments of the first aspect of the present application, comprising:

[0017] Using a three-dimensional braiding method to braid aluminum wires into a 3D aluminum scaffold, filling the polyetheretherketone mixed powder into the 3D aluminum scaffold and performing hot pressing to obtain a composite material 3D aluminum scaffold;

[0018] Placing the composite material 3D aluminum scaffold at the bottom of a hot pressing mold, alternately laying each carbon fiber polyetheretherketone prepreg and each polyetheretherketone film above the composite material 3D aluminum scaffold according to a preset layering sequence, and then placing another composite material 3D aluminum scaffold on top of the hot pressing mold;

[0019] Performing hot pressing on the hot pressing mold, and when the hot pressing mold cools to room temperature, opening the mold and taking out the specimen;

[0020] By means of cutting and an etching solution method, milling off the polymer coating the 3D aluminum scaffold in the composite material 3D aluminum scaffolds on the upper and lower surfaces of the specimen to obtain the surface porous composite material.

[0021] The third aspect of the present application provides an implant, comprising: the preparation material of the implant comprises the novel carbon fiber-reinforced surface porous composite material as described in the third embodiment of the first aspect of the present application.

[0022] As can be seen from the above, the present application provides a novel carbon fiber reinforced surface porous composite material and a preparation method thereof, comprising two functionalized porous structures, a plurality of carbon fiber polyetheretherketone (CF / PEEK) prepregs and a plurality of polyetheretherketone (PEEK) films, wherein each CF / PEEK prepreg and each PEEK film are alternately layered between the two functionalized porous structures in a preset order. The surface porous composite material provided by the present application uses two functionalized porous structures as the upper and lower surfaces, and the porous structure that penetrates realizes the interconnection between the internal material of the surface porous composite material and the external environment. At the same time, the functionalized porous structure is a polyetheretherketone mixture, and the polyetheretherketone mixture can better realize the functionality of the corresponding material (such as mixing with HA to improve biological activity and bone induction ability) by mixing polyetheretherketone with different materials. In addition, the mechanical properties of the surface porous composite material are mainly determined by the relative thickness of the CF / PEEK prepreg and the functionalized porous structure and the preset plying order. Therefore, the present application can adjust the relative thickness of each layer and the plying order of the CF / PEEK prepreg and the PEEK film to better match the different mechanical properties of tensile, compression and bending modulus, thereby achieving a balance between the surface porous structure and mechanical properties and functionality, and showing great potential in the fields of artificial bone repair, catalysts, adsorbents, insulating materials, and electromagnetic shielding. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 A schematic diagram of the structural decomposition of a surface porous composite material provided in an embodiment of the present application;

[0025] Figure 2 A diagram showing the preparation process of a surface porous composite material provided in an embodiment of the present application;

[0026] Figure 3 A diagram showing the preparation process of a functional porous structure provided in an embodiment of the present application;

[0027] Figure 4 A schematic diagram of the structure of a 3D aluminum bracket provided in an embodiment of the present application;

[0028] Figure 5 A CFR-SP-PEEK / HA specimen provided in an embodiment of the present application;

[0029] Figure 6Schematic diagram of a CFR-SP-PEEK / HA provided by an embodiment of the present application;

[0030] Figure 7 Failure sequence diagram of different material single plates of a CFR-SP-PEEK / HA under different conditions provided by an embodiment of the present application;

[0031] Figure 8 FTIR energy spectrum and XRD pattern of a CFR-SP-PEEK / HA provided by an embodiment of the present application;

[0032] Figure 9 Three-dimensional reconstruction and cross-sectional view of a CFR-SP-PEEK / HA provided by an embodiment of the present application;

[0033] Figure 10 Stress-strain curve, equivalent tensile strength and modulus of a CFR-SP-PEEK / HA obtained through tensile test, theoretical model and numerical simulation, and progressive failure process obtained through numerical simulation provided by an embodiment of the present application;

[0034] Figure 11 Magnified view of the tensile fracture surface of a CFR-SP-PEEK / HA provided by an embodiment of the present application;

[0035] Figure 12 Stress-strain curve, equivalent compressive strength and modulus of a CFR-SP-PEEK / HA obtained through compression test, theoretical model and numerical simulation, and progressive failure process obtained through numerical simulation provided by an embodiment of the present application;

[0036] Figure 13 Another magnified view of the tensile fracture surface of a CFR-SP-PEEK / HA provided by an embodiment of the present application;

[0037] Figure 14 Tensile modulus of a CFR-SP-PEEK / HA in the 1 direction and 2 direction, and change of strength with the relative thickness of 0° CF / PEEK and PEEK / HA-S during tensile and compression in the 1 direction provided by an embodiment of the present application;

[0038] Figure 15 Variation law of the flexural modulus of a CFR-SP-PEEK / HA with the relative thickness of PEEK / HA-S provided by an embodiment of the present application. Detailed implementation manners

[0039] In the following description, specific details such as specific system architectures, technologies, etc. are presented for the purpose of illustration rather than limitation, so as to thoroughly understand the embodiments of the present application. However, those skilled in the art should clearly understand that the present application can also be implemented in other embodiments without these specific details. In other cases, detailed descriptions of well-known systems, devices, circuits, and methods are omitted to avoid unnecessary details from interfering with the description of the present application.

[0040] It should be understood that when used in this specification and the appended claims, the term "comprising" indicates the presence of the described features, wholes, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components, and / or their combinations.

[0041] It should also be understood that the terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. As used in the specification of the present application and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an", and "the" are intended to include the plural forms.

[0042] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the scope of protection of the present application.

[0043] Many specific details are set forth in the following description in order to provide a thorough understanding of the present application, but the present application may also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the connotation of the present application, so the present application is not limited by the specific embodiments disclosed below.

[0044] Embodiment 1

[0045] The embodiment of the present application provides a novel carbon fiber-reinforced surface porous composite material. As Figure 1 shown, the surface porous composite material includes:

[0046] Two functionalized porous structures 100 located on the upper and lower surfaces of the surface porous composite material, a plurality of carbon fiber polyether ether ketone (CF / PEEK) prepregs 110, and a plurality of polyether ether ketone (PEEK) films 120. Each CF / PEEK prepreg 110 and each PEEK film 120 are alternately laid between the two functionalized porous structures 100 according to a preset layup sequence;

[0047] The functionalized porous structure 100 is a polyetheretherketone mixture after hot pressing. The CF / PEEK prepreg 110 is a first CF / PEEK prepreg 111 with a laying direction of 0° or a second CF / PEEK prepreg 112 with a laying direction of 90°.

[0048] In one embodiment, carbon fiber (CF) is a reinforcing fiber with excellent performance. Compared with short carbon fibers, continuous CF-reinforced resin-based composites have more excellent mechanical properties. Generally, the elastic modulus of carbon fiber-reinforced polyetheretherketone (CFR / PEEK) composites is close to that of human cortical bone, which depends on the direction, quantity, and manufacturing method of the carbon fibers. CFR / PEEK inherits the advantages of PEEK and improves its mechanical properties, and is considered a promising candidate material to replace metal materials. Therefore, in the embodiments of the present application, CF / PEEK is used as the prepreg, and a PEEK film 120 is used as a transition layer between the functionalized porous structure 100 and the CF / PEEK prepreg 110 to achieve good transition between different material interfaces.

[0049] Optionally, the surface porous composite material includes 4 layers of PEEK films 120 and 7 layers of CF / PEEK prepregs 110. The preset laying sequence of the 4 layers of PEEK films 120 and 7 layers of CF / PEEK prepregs 110 is: P / 0 / 90 / P / 0 / 90 / 0 / P / 90 / 0 / P, where P represents the PEEK film 120, and 0 and 90 respectively represent the first CF / PEEK prepreg 111 and the second CF / PEEK prepreg 112 with laying directions of 0° and 90°. Alternatively, in other embodiments, the quantity and preset laying sequence of each polyetheretherketone film 120 and CF / PEEK prepreg 110 can be adjusted according to actual needs to obtain appropriate mechanical properties, which are not limited herein.

[0050] In one embodiment, the functionalized porous structure 100 is a network structure provided with a plurality of through holes, and the aperture of each through hole is 0.6 mm. The model of the CF / PEEK prepreg 110 is Cetex TC1200 PEEKAS-4, and the thickness is 0.155 mm. The model of the PEEK film 120 is 5600G, and the thickness is 0.157 mm. Alternatively, in other embodiments, the relative thickness of the functionalized porous structure 100 and the CF / PEEK prepreg 110 can be adjusted according to actual needs to obtain appropriate mechanical properties, which are not limited herein.

[0051] Optionally, two functionalized porous structures are disposed on both sides of each CF / PEEK prepreg 110 and PEEK film 110, forming a composite material with a surface porous structure, so that the surface porous composite material has a large specific surface area and a rich pore structure, and has a wider application range. At the same time, by mixing polyetheretherketone (PEEK) powder with different types of functional material particles and hot pressing to form different polyetheretherketone mixtures, the functional materials in the polyetheretherketone mixture can be adjusted according to the requirements of the application field and application environment, and a surface porous composite material with corresponding functions can be obtained.

[0052] Optionally, when the surface porous composite material is used for orthopedic implants, the polyetheretherketone mixture includes: PEEK and a bioactive material, wherein the bioactive material is any one of hydroxyapatite (HA), calcium phosphate ceramics, bioglass, zirconia, silicon nitride, and aluminate ceramics.

[0053] Specifically, calcium phosphate ceramic materials include HA and β-tricalcium phosphate (β-TCP), etc. These materials have high thermal stability and can maintain biological activity at high temperatures; bioglass is a glass material with biological activity and can maintain its biological activity at high temperatures; zirconia is a ceramic material with a high melting point, excellent thermal stability and biocompatibility, and still has biological activity at high temperatures; silicon nitride is a ceramic material with a high melting point and high hardness and can maintain its biological activity at high temperatures; aluminate ceramics are high-temperature ceramic materials with excellent thermal stability and biocompatibility and can maintain their biological activity at high temperatures.

[0054] In one embodiment, when the polyetheretherketone mixture includes PEEK and HA, the obtained surface porous composite material is called CFR-SP-PEEK / HA composite material, and the functionalized porous structure 100 is called PEEK / HA-S. The mass fraction of HA is 20%, and the particle size is 20 nm to ensure sufficient in vitro osteogenic performance and mechanical properties at the same time. The reticular PEEK / HA-S has multiple pores, which can provide a through reticular structure for body fluid transport and bone cell growth. The HA on the material surface can improve biological activity and bone induction ability. At the same time, the surface porous composite material is designed with layering through CF / PEEK prepregs 110 and PEEK films 120 in different directions, and the relative thickness of each layer is adjusted to change the mechanical properties of the surface porous composite material, so that it matches the elastic modulus of the surrounding bone tissue, which is beneficial to reducing the stress shielding effect caused by femoral head necrosis and bone resorption.

[0055] Optionally, the porous structure of the surface porous composite material has a large specific surface area and a rich pore structure, so it has a wide range of applications in catalysts. For example, porous ceramics, porous metals, etc. are all commonly used catalyst materials. These porous materials can optimize the performance of the catalyst and the selectivity of the application by regulating structural parameters such as pore size and porosity. The polyetheretherketone mixture includes: PEEK and a catalyst material, where the catalyst material is any one of alumina, aluminosilicate, copper catalyst, molybdenum catalyst, and platinum group metal catalyst.

[0056] Specifically, alumina is a common high-temperature catalyst that can maintain stability and catalytic activity at high temperatures and is commonly used in catalytic cracking, hydrogenation, and other reactions; aluminosilicate is a catalyst with good high-temperature stability and catalytic activity and has a wide range of applications, including automotive exhaust treatment, chemical reactions, catalytic cracking, and other fields; copper catalyst exhibits good catalytic activity and stability in oxidation reactions and is therefore widely used in high-temperature oxidation reactions; molybdenum catalyst has excellent high-temperature stability and catalytic activity and is therefore widely used in petrochemical industry, catalytic cracking, oxidation reactions, and other fields; platinum group metal catalyst exhibits excellent catalytic performance and stability under high-temperature conditions and is therefore widely used in alkylation, hydrogenation, oxidation, and other reactions.

[0057] Optionally, the porous structure of the surface porous composite material can control its adsorption performance by regulating structural parameters such as pore size and porosity, so it has a wide range of applications in adsorbents. For example, porous carbon materials, porous polymer materials, etc. are all commonly used adsorbent materials. These porous materials can be used in wastewater treatment, gas purification, solid waste treatment, and other aspects in industrial processes such as separation, purification, and concentration. The polyetheretherketone mixture includes: PEEK and an adsorbent material, where the adsorbent material is any one of activated carbon, zeolite, activated alumina, and titanium oxide.

[0058] Specifically, activated carbon is a commonly used adsorbent with good adsorption performance and high-temperature stability and has a wide range of applications, such as in high-temperature gas purification, desulfurization, denitrification, and other fields; zeolite is a high-temperature stable adsorbent that can adsorb gases at high temperatures and has excellent separation performance and is widely used in high-temperature gas separation, gas purification, catalyst support, and other fields; activated alumina is a high-temperature stable adsorbent with good adsorption performance and chemical stability and is commonly used in high-temperature gas purification, denitrification, and other fields; titanium oxide is a high-temperature stable adsorbent with good adsorption performance and chemical stability and has a wide range of applications, such as in high-temperature gas purification, denitrification, and other fields.

[0059] Optionally, the porous structure of the surface porous composite material can control its insulation performance by controlling structural parameters such as porosity, so it has a wide range of applications in insulation materials. For example, porous ceramics, porous polymer materials, etc. are all commonly used insulation materials. These porous materials can be used for insulation protection in harsh environments such as high temperature and high pressure. The polyetheretherketone mixture includes: PEEK and an insulation material, where the insulation material is any one of ceramic materials, silicone rubber, glass fiber, ceramic fiber, and silicone glue.

[0060] Specifically, high-temperature ceramic materials such as alumina ceramics and silicon nitride ceramics have good high-temperature insulation performance and heat resistance, and can be used for high-temperature electrical insulation and heat insulation applications; silicone rubber is a high-temperature insulation material with good high-temperature resistance and electrical insulation performance, and can be used in fields such as high-temperature cable insulation and electronic component encapsulation; glass fiber has excellent insulation performance and high-temperature resistance, and can be used for applications such as high-temperature cable insulation, heat insulation materials, and electronic component insulation; ceramic fiber has excellent high-temperature insulation performance and heat resistance, and can be used in fields such as high-temperature heat insulation, furnace lining, and high-temperature electrical insulation; silicone glue is a high-temperature insulation material with good high-temperature resistance and electrical insulation performance, and can be used for applications such as high-temperature electronic packaging and cable insulation.

[0061] Optionally, the porous structure of the surface porous composite material has great application potential in electromagnetic shielding. Its pore structure and surface morphology can affect its electromagnetic properties. By adjusting the pore structure and surface morphology, absorption and reflection of electromagnetic radiation in specific frequency bands can be achieved. In electromagnetic shielding, porous materials can be used as electromagnetic wave absorption materials. Porous materials have the characteristics of high specific surface area and low density, which can increase the contact area between the material and electromagnetic waves and improve the absorption efficiency. In addition, porous materials can control the absorption frequency and absorption intensity of the material by adjusting parameters such as pore structure and pore distribution, so as to achieve effective absorption of electromagnetic waves in specific frequency bands.

[0062] In addition, porous materials can also be used as the substrate of electromagnetic shielding materials. By plating a metal layer or a conductive polymer material on the surface of the porous material, an electromagnetic shielding material with high conductivity can be formed. The pore structure and surface morphology of the porous material can affect the reflection and transmission of electromagnetic waves, thereby affecting the electromagnetic shielding effect. By reasonably designing the pore structure and surface morphology of the porous material, control of the reflection and transmission of electromagnetic waves in specific frequency bands can be achieved, and the electromagnetic shielding effect can be improved. The polyetheretherketone mixture includes: PEEK and an electromagnetic shielding material, where the electromagnetic shielding material is any one of copper alloys, nickel-based alloys, conductive ceramic materials, conductive coating materials, and carbon fibers.

[0063] Specifically, copper alloy is a metallic material with excellent electrical conductivity and shielding performance. It also has high thermal stability and corrosion resistance, making it suitable for applications in high-temperature environments. Nickel-based alloy is an alloy material with high temperature resistance and corrosion resistance. It has good electrical conductivity and relatively good shielding performance, and is widely used in high-temperature environments. Conductive ceramic materials have excellent electrical conductivity and high-temperature stability, and can be used for electromagnetic shielding in high-temperature environments, such as titanium dioxide, silicon nitride, etc. Conductive coating materials are materials that combine electrical conductivity and high-temperature stability. Commonly used conductive coating materials include conductive polymers, conductive metal oxides, etc. Carbon fiber composite materials have excellent electrical conductivity and high-temperature stability, and are widely used in fields such as aerospace and automotive.

[0064] As can be seen from the above, the embodiment of the present application provides a novel carbon fiber-reinforced surface porous composite material. Using two functionalized porous structures 100 as the upper and lower surfaces, the through-hole porous structure realizes the intercommunication between the internal material and the external environment. At the same time, the functionalized porous structure 100 is a polyether ether ketone mixture, and this polyether ether ketone mixture can better realize the functionality of the corresponding material by mixing polyether ether ketone with different materials (such as mixing with HA to improve bioactivity and bone induction ability). In addition, the mechanical properties of the surface porous composite material are mainly determined by the relative thickness of the CF / PEEK prepreg 110 and the functionalized porous structure 100 and the preset lay-up sequence. By adjusting the relative thickness of each layer and the lay-up sequence of the CF / PEEK prepreg 110 and the PEEK film 120, it can better match the mechanical properties with different tensile, compressive, and bending moduli, achieving the balance of the surface porous structure, mechanical properties, and functionality, and showing great potential in fields such as artificial bone repair, catalysts, adsorbents, insulating materials, and electromagnetic shielding.

[0065] Embodiment 2

[0066] The embodiment of the present application provides a preparation method for preparing the novel carbon fiber-reinforced surface porous composite material as described in Embodiment 1, as Figure 2 shown, the surface porous composite material is prepared by the method of composite 3D aluminum scaffold preparation - prepreg lay-up - hot pressing - solution corrosion. The specific operations are as follows:

[0067] S210 Composite 3D aluminum scaffold preparation: Using the three-dimensional braiding method to braid aluminum wires into a 3D aluminum scaffold, filling the polyether ether ketone mixed powder into the 3D aluminum scaffold and performing hot pressing to obtain the composite 3D aluminum scaffold;

[0068] In one embodiment, when the polyether ether ketone mixed powder includes PEEK powder and HA powder, as Figure 3 and 4 shown, the specific preparation process of this composite 3D aluminum scaffold includes:

[0069] S211 3D braiding of aluminum wire: Use a 3D braiding machine to braid aluminum wires with a diameter of 0.6 mm and a purity of ≥99.9% into a 3D aluminum scaffold. The geometric parameters of the 3D braided aluminum scaffold are as Figure 4 shown. In the figure, (a) is the front view, (b) is the left view, (c) is the top view, and (d) is the isometric view. The porosity of the aluminum scaffold depends on the diameter d of the aluminum wire, the net distances between adjacent warp and weft wires are m and n respectively, the length l, width a, and height h of the 3D braided aluminum scaffold. Therefore, the porosity ρ can be calculated by the ratio of the pore volume V p in the unit cell to the total volume V t :

[0070]

[0071] S212 Powder filling: Use the ball milling and blending method to mix PEEK powder and HA powder evenly. Dry the evenly mixed powder in a strong convection oven at 170 °C for 8 hours to remove excess moisture and other impurities. Fill the dried mixed powder into the 3D aluminum scaffold and vibrate it for 1 hour at a frequency of 5 Hz by a multi-purpose vibrator (model: HY-5B) to ensure that the mixture is fully compacted in the pores.

[0072] S213 Hot pressing: Place the assembled mold into a hot press with a set heating program, and complete the pressing of the composite material according to the established process route. The hot pressing parameters and the changing trends of temperature and pressure over time are as Figure 3 (c) shown. The heating rate is 2.5 °C / min, the forming temperature is 365 °C, the forming pressure is 2 MPa, and the cooling rate is 0.5 °C / min. Before reaching the forming temperature, the heating and pressurizing method is pressureless heating to avoid crushing the 3D aluminum scaffold. After reaching the forming temperature, raise the pressure to 2 MPa and maintain it for 50 minutes to ensure the densification of the material, good interface, and full crystallization of the PEEK matrix, and obtain the composite 3D aluminum scaffold (PEEK / HA-3D aluminum scaffold).

[0073] Optionally, the 3D aluminum scaffold in the PEEK / HA-3D aluminum scaffold can be etched away by an alkaline solution etching method to form a fully penetrated grid structure, obtaining PEEK / HA-S.

[0074] S220 Prepreg layup: Place the composite 3D aluminum scaffold at the bottom of the hot pressing mold, alternately lay each CF / PEEK prepreg 110 and each PEEK film 120 above the composite 3D aluminum scaffold according to the preset layup sequence, then place another composite 3D aluminum scaffold on the top of the hot pressing mold, and cover the mold to prepare for hot pressing;

[0075] S230 Hot pressing: Perform hot pressing on the hot pressing mold. The changing trends of temperature and pressure over time are as shown in Figure 2 (c). The heating rate is 2.5 °C / min, the heat preservation time is 30 min, the processing temperature is 380 °C, the pressure before reaching the forming temperature is 0.3 MPa to ensure sufficient contact between layers of materials and expel the gas in the hot pressing mold. The forming pressure is 2 MPa, and the cooling rate is 0.5 °C / min. After the hot pressing mold is cooled to room temperature, open the mold and take out the specimen;

[0076] S240 Solution corrosion: Mill off the polymer coating the 3D aluminum bracket in the composite materials on the upper and lower surfaces of the specimen by cutting and corrosion solution methods to fully expose it, and obtain the surface porous composite material.

[0077] Optionally, the corrosion solution is replaced with an acidic solution (hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, etc.) and a basic solution (sodium hydroxide, potassium hydroxide, etc.) according to the acid and alkali resistance types of the bioactive particles.

[0078] In one embodiment, cut the specimen into standard parts, mill off 0.1 mm from the upper and lower layers, and use a NaOH solution with a concentration of 3 mol / L to corrode the 3D aluminum bracket to form a completely penetrated grid structure (3 mol / L, room temperature, 72 h). Then ultrasonically clean it in acetone, absolute ethanol, and deionized water solution for 30 min respectively, and then put it in an oven at 80 °C for drying for 12 hours.

[0079] As can be seen from the above, the preparation method provided by the embodiment of the present application prepares the novel carbon fiber-reinforced surface porous composite material as described in Example 1. Using the two functionalized porous structures 100 as the upper and lower surfaces, the penetrated porous structure realizes the intercommunication between the internal material and the external environment. At the same time, the functionalized porous structure 100 is a polyether ether ketone mixture. By mixing PEEK with different materials, the functionality of the corresponding materials can be better realized (such as mixing with HA to improve bioactivity and osteoinductive ability). In addition, the mechanical properties of the surface porous composite material are mainly determined by the relative thickness of the CF / PEEK prepreg 110 and the functionalized porous structure 100 and the preset ply sequence. By adjusting the relative thickness of each layer and the ply sequence of the CF / PEEK prepreg 110 and the PEEK film 120, it can better match the mechanical properties with different tensile, compressive, and bending moduli, achieving both surface porous structure and mechanical properties and functionality, and showing great potential in the fields of artificial bone repair, catalysts, adsorbents, insulating materials, and electromagnetic shielding.

[0080] Example 3

[0081] In the embodiments of the present application, experiments are conducted to verify and demonstrate the effects of a CFR-SP-PEEK / HA composite material provided in Embodiment 1. The specific experimental process is as follows:

[0082] Mechanical testing experimental environment: A universal electronic testing machine is used for quasi-static mechanical tests. Tensile and compression tests are carried out according to ASTM D3039 and ASTM D6641 standards respectively. Three samples are tested in each batch. The loading method is displacement loading, and the loading speed is 0.2 mm / min. The test environment temperature is 20 - 25 °C.

[0083] Since the mechanical properties of the porous PEEK / HA-S single board on the surface of the CFR-SP-PEEK / HA composite material are poorer than those of the CF / PEEK single board, during testing, the specimen cannot be cut into a traditional rectangular shape and then subjected to tensile and compression tests by attaching strengthening pieces. Instead, the specimen is cut into a dumbbell shape, and then strengthening pieces of the same size are attached to both sides of the specimen to increase the clamping area and clamping force, ensuring that the fracture position of the specimen is in the gauge section. The width of the specimen end is 16 mm, the thickness is 3.2 mm, and the clamping lengths are 40 mm (tensile test) and 63 mm (compression test) respectively. The detailed dimensions of the specimen are as Figure 5 shown Figure 5 (a) is the tensile dimension Figure 5 (b) is the dimension of the compression test piece. The equivalent strength and modulus of the CFR-SP-PEEK / HA composite material are calculated using the load-displacement curve. Each sample contains 3 specimens, and the final result takes the average value and standard deviation of the 3 specimens.

[0084] Numerical simulation of the CFR-SP-PEEK / HA composite material: In order to more deeply evaluate and explore the quasi-static mechanical behavior and failure mode of the CFR-SP-PEEK / HA composite material, Abaqus / CAE 6.14 is used for numerical simulation. Considering that the CFR-SP-PEEK / HA composite material is composed of a PEEK film, CF / PEEK prepreg, and PEEK / HA-S respectively, different constitutive models and failure modes are assigned to the 3 materials respectively. The continuous shell element (SC8R) is used to define the cross-sectional properties of the CFR-SP-PEEK / HA composite material. Since different materials are formed under high temperature and high pressure and have good interfacial properties between the materials. Therefore, the interfacial properties between different materials are not considered.

[0085] The progressive failure analysis of CF / PEEK single plates was carried out by using the Hashin failure criterion and the energy-based evolution criterion. The two-dimensional Hashin failure criterion was introduced in ABAQUS. The failure modes were divided into four types: longitudinal tension (tension in the fiber direction), longitudinal compression (compression in the fiber direction), transverse tension (tension perpendicular to the fiber direction), and transverse compression (compression perpendicular to the fiber direction). By calculating the stress-strain relationship of the damaged CF / PEEK single plate, the following two-dimensional Hashin damage initiation criteria were obtained: fiber tension, fiber compression, matrix tensile cracking, and matrix compression.

[0086] Subsequently, the damage evolution parameter was defined based on energy, and the fracture energy corresponding to the four modes was input. The simulation parameters of the CF / PEEK single plate are shown in Table 1. For the PEEK film, the mechanical response was defined by the ideal elastic-elastoplastic-perfectly plastic constitutive model, and the complete plasticity of the material was used as the sign of material failure. For the elastoplastic stage, the true stress and plastic strain of the material were input, and one data point was taken every 20 data points. Its mechanical parameters are shown in Table 1. For PEEK / HA-S, since it shows different mechanical responses under tensile and compressive loads. Therefore, when the composite material is subjected to different types of loads, different material constitutive models are input. The specific method is that when subjected to tensile loads, the material exhibits elastic-brittle behavior, and brittle cracking is used as its failure mode, and the maximum tensile strain reaching the ultimate strain is used as the failure criterion of the material; when subjected to compressive loads, the material exhibits elastic-elastoplastic-perfectly plastic behavior and the complete yield of the material is used as the failure criterion of the material. Its mechanical parameters are shown in Table 1.

[0087]

[0088] Table 1. Mechanical properties of unidirectional CF / PEEK prepreg, PEEK film, and porous PEEK / HA-S

[0089] When the CFR-SP-PEEK / HA composite material is subjected to tensile loads, the mechanical properties of the PEEK / HA-S on its surface are weaker than those of the CF / PEEK single board. To ensure that the composite material fails in the gauge section, the tensile model is designed as a dumbbell shape, while the compression load model is rectangular (although the tested specimens are dumbbell-shaped, by attaching reinforcing aluminum sheets at the arc positions to ensure that the compression failure position is in the middle position, and to avoid the influence of stress concentration at the arc positions on the compression results, so the compression model is designed as a rectangle). Reference points are established at the center positions of the left and right cross-sections and the reference points are coupled with the cross-sections. A fixed constraint is applied to the left reference point, and a displacement constraint is applied to the right side while restraining the displacements in the 2 and 3 directions on the material surface. When the CFR-SP-PEEK / HA composite material is subjected to bending loads, the ratio of the length:span:width:thickness of the model is taken as 40:32:5:2, and the contact property is general contact. The equivalent strength and modulus of CFR-SP-PEEK / HA are calculated by monitoring the reaction forces and displacements of the reference points.

[0090] Theoretical model of CFR-SP-PEEK / HA composite material: The CFR-SP-PEEK / HA composite material prepared by hot pressing the PEEK / HA-3D aluminum bracket, CF / PEEK prepreg and PEEK film and then corroding with an alkaline solution, as Figure 6 shown in the figure. In the figure, (a) is the isometric view of the CFR-SP-PEEK / HA composite material, (b) is the schematic diagram of the laminated single board, (c) is the enlarged cross-sectional view, and (d) is the schematic diagram of the straight normal before and after the bending load. The performance of the CFR-SP-PEEK / HA composite material is related to the material properties of each layer of single board and the laying method of each layer of single board. Single-layer composite materials are usually not used alone, but as the basic unit of composite materials. The classical lamination theory (CLT) is used to analyze the force-deformation relationship and stiffness coupling effect of composite materials, including the strain, displacement and bending of composite materials under the action of forces. This method is based on the isotropic plate theory, and the main difference lies in the stress-strain relationship of thin plates. The following assumptions are made for the classical lamination theory:

[0091] (1) Assumption of unchanged straight normal: a Assume a primary straight line perpendicular to the mid-plane of the composite material. After the composite material is subjected to tension and bending, it still remains straight and perpendicular to the mid-plane. b The straight line perpendicular to the mid-plane of the plate before deformation remains perpendicular after deformation, and the length remains unchanged.

[0092] (2) Assumption of plane stress in each layer: Each single layer in the composite material is approximately in a plane stress state, and the normal stress in the thickness direction is very small compared with other stresses and can be ignored.

[0093] (3) Assumption of interlayer deformation consistency: The adhesive layer between each single layer of the composite material is very thin. The displacements on both sides of the single layer boundary are continuous, and there is no slippage or relative displacement between layers.

[0094] The ply stacking sequence of CFR-SP-PEEK / HA composite material is 1, 2, 3, … k, k + 1, n layers from bottom to top, as shown in Figure 6 (c). The stiffness matrix of the composite material is derived from the total resultant force and resultant moment acting on the CFR-SP-PEEK / HA composite material, and is further simplified into the ABD matrix form. Combining with the thickness t of the k-th layer k the ABD matrix regarding thickness and cross-section position is obtained. For the single layer of the composite material shown in Figure 6 (b), the thickness in the 3 direction (thickness direction z) of its composite single board is much smaller than the dimensions in the two in-plane directions 1 and 2 (x and y directions). The stress-strain relationship of the orthotropic composite material single layer under plane stress state can be obtained, and then the stress-strain relationship of the simple composite material in any direction can be obtained. Combining the stiffness matrices of different composite single boards and the ABD matrix regarding thickness and cross-section position to calculate the overall stiffness matrix, the in-plane effective modulus E x , E y and the out-of-plane effective bending modulus E x b are obtained, and the constitutive equation is obtained.

[0095] Analysis of failure modes based on constitutive models: Analyze the stress of each layer of CFR-SP-PEEK / HA composite materials, calculate the strength ratio of each ply using the strength ratio equation, and the ply with the minimum strength fails first. When the CFR-SP-PEEK / HA composite material is subjected to uniaxial tensile load, the PEEK / HA-S single ply, PEEK film, and CF / PEEK single plies in different directions jointly bear the load. Through calculation, the failure modes of the CFR-SP-PEEK / HA composite material are successively the tensile brittle fracture of PEEK / HA-S, the tensile failure of 90° CF / PEEK, the tensile failure of 0° CF / PEEK, and the complete plastic failure after the tensile yield of PEEK. The tensile brittle failure of PEEK / HA-S is the first yield point of the CFR-SP-PEEK / HA composite material. Calculate the first yield load using the maximum linear strain theory (the second strength theory), and use the shape change energy density theory (the fourth strength theory) and the Hill-Tsai (S.W.Tsai) strength theory to check the strength of the PEEK film and CF / PEEK single plies in different directions respectively. After the tensile failure of PEEK / HA-S, the 90° CF / PEEK prepreg subsequently undergoes tensile failure. Calculate the second yield strength theoretical expression using the Hill-Tsai (S.W.Tsai) strength theory. Subsequently, check the strength of the PEEK film and 0° CF / PEEK prepreg, and calculate the strength at the failure of the remaining single plies in the same way. The failure order of different material single plies of the CFR-SP-PEEK / HA composite material under tensile load is as Figure 7 (a) shown.

[0096] When the CFR-SP-PEEK / HA composite material is subjected to uniaxial compressive load, the PEEK / HA-S, PEEK film, and CF / PEEK single plies jointly bear the load. Through calculation, it can be seen that the failure order of CFR-SP-PEEK / HA is the compressive failure of 0° CF / PEEK single ply, the compressive yield of PEEK / HA-S single ply, the compressive failure of 90° CF / PEEK single ply, and the compressive yield of PEEK film, as Figure 7(as shown in (b). However, when the 0℃F / PEEK single board is compressed and damaged, the bearing capacity of the composite material reaches the limit state. Therefore, the subsequent progressive failure of the CFR-SP-PEEK / HA composite material is not calculated. When the symmetric CFR-SP-PEEK / HA composite material is subjected to a bending load, the neutral axis coincides with the symmetry axis of the cross-section, and the PEEK / HA-S single board on the surface of the composite material exhibits tensile brittleness and compressive elastoplasticity, and the tensile failure strain is small. Therefore, when the bending tensile strain of the lower-side PEEK / HA-S reaches its ultimate tensile strain, the PEEK / HA-S undergoes tensile fracture failure. Therefore, the tensile fracture of the PEEK / HA-S on the lower-side cross-section of the composite material under the bending load is taken as the start of the failure. The second strength theory is used to predict the failure of the PEEK / HA-S under the bending load.)

[0097] Experimental conclusions and analysis:

[0098] 1. Component analysis of the CFR-SP-PEEK / HA composite material:

[0099] Figure 8 (a) is the FTIR Fourier transform infrared spectrogram of the CFR-SP-PEEK / HA composite material. The strong peak at 1652 cm -1 originates from the stretching vibration of the C=O carbonyl group, and the bands at 1598 cm -1 and 1490 cm -1 are the in-plane vibration bands of benzene; the two C-H vibration bands at 837 cm -1 and 766 cm -1 belong to the sub-bands of the out-of-plane bending vibration absorption of benzene, and among them, 837 cm -1 is for the para-substituted aromatic ring. These are all characteristic peaks of PEEK. The P-O vibration band at 1031 cm -1 confirms the presence of the PO4 group. In addition, the absorption peak at 3571 cm -1 can be attributed to the stretching vibration of the hydroxyl group of HA.)

[0100] The X-ray diffraction spectrogram of the CFR-SP-PEEK / HA composite material is as shown in Figure 8 (b), further confirming that HA has been successfully incorporated into the composite material. The 2θ peaks at 18.7°, 20.8° and 22.9° are the characteristic peaks of PEEK, the obvious (002) reflection plane of CF is located at about 25.4°, and the characteristic peaks of HA appear at 31.8°, 40.0°, 46.7°, 49.5° and 53.9°. In addition, there are no new peaks in the CFR-SP-PEEK / HA composite material except for the inherent peaks of PEEK, HA and CF themselves. This indicates that no new crystal phases are formed among the three materials during the preparation of the composite material, and the crystal structure has not changed.)

[0101] 2. Pore structure of CFR-SP-PEEK / HA composite material:

[0102] The CFR-SP-PEEK / HA composite material was cut into 12 mm × 12 mm × 3 mm. The cross-sectional view of the specimen was obtained by Micro-CT scanning. The voxel resolution was 5.0 μm. The scanner was set at 60 kVp and the peak current was 166 μA. The scanning data was imported into the software Mimics 21.0 to establish a real CFR-SP-PEEK / HA model. The CFR-SP-PEEK / HA composite material was segmented from the pores using a global threshold (30 - 254 GV), which was kept consistent in all evaluations. The scanning results are as Figure 9 shown.

[0103] By observing the scanned and reconstructed model, it was found that the CFR-SP-PEEK / HA composite material was mainly composed of porous layers on the upper and lower surfaces and a solid layer in the middle, and they were tightly connected at the contact positions without obvious pores, indicating good performance at the interfaces between different single layers. Figure 9 In [the figure], by scanning the cross-section of the composite material (1-1), it was found that the pores of the porous PEEK / HA-S on the material surface were evenly distributed, and the pores in different directions were tightly connected, forming a three-dimensional through-porous surface. There were a few bright spots on the cross-sectional view, which were caused by particle agglomeration between nano-HAs. By observing the cross-sectional view at the 2-2 position, it could be seen that the middle layers were closely arranged without pores, and the carbon fibers were tightly arranged at 90°. The cross-sectional view at the 3-3 position showed good interfaces between the porous PEEK / HA-S on the surface and the middle CF / PEEK single layer without obvious defects. Generally, the CFR-SP-PEEK / HA composite material was prepared by the method of PEEK / HA-3D aluminum scaffold preparation - prepreg layup - hot pressing - alkaline solution corrosion, realizing the porous structure on the material surface and the layup design at the middle position.

[0104] 3. Mechanical properties of CFR-SP-PEEK / HA composite material

[0105] The stress-strain curves, equivalent tensile strength, and elastic modulus of the CFR-SP-PEEK / HA composite material obtained by tensile testing, numerical simulation, and theoretical model are as Figure 10(as shown in (a) - (b)). It can be seen that the CFR - SP - PEEK / HA composite material exhibits elastic - brittle properties when subjected to tensile loads. When the ultimate load is reached, its load - bearing capacity drops rapidly, and the load - bearing capacity completely fails. The measured values, theoretical values, and simulation values of the equivalent tensile modulus of the CFR - SP - PEEK / HA composite material are in good agreement, with a maximum error not exceeding 3%. This indicates that the classical laminate theory and numerical simulation methods can effectively predict the equivalent tensile modulus of the CFR - SP - PEEK / HA composite material composed of CF / PEEK, PEEK, and PEEK / HA - S. The experimental values of the equivalent tensile strength of the CFR - SP - PEEK / HA composite material are in good agreement with the simulation values, and the simulation values are slightly larger than the theoretical values, but the maximum error does not exceed 5%. Therefore, it is considered that numerical simulation and theoretical models can accurately predict the tensile strength and modulus of the CFR - SP - PEEK / HA composite material. Through numerical simulation, the failure mode of the CFR - SP - PEEK / HA composite material under tensile loads was analyzed and predicted as shown in Figure 10 (c). It can be seen that the failure sequence is the tensile cracking of PEEK / HA - S, the tensile failure of the 0° and 90°F / PEEK single - ply matrices, and the tensile failure of the 0°F / PEEK fibers, which is basically consistent with Figure 7 (a) The predicted failure sequence of the CFR - SP - PEEK / HA composite material.

[0106] By taking SEM scans of the tensile fracture surface as shown in Figure 11 . It was found that the PEEK / HA - S and CF / PEEK prepregs connected by the PEEK film were completely integrated, which was the result of the complete melting of the PEEK matrix during the hot - pressing process. In addition, the fracture of the 0°F / PEEK fibers and matrix, the tensile failure of the 90°F / PEEK matrix, and the tensile cracking of PEEK / HA - S were observed, which were basically consistent with the failure modes predicted in the theoretical model and numerical simulation.

[0107] The stress - strain curves and equivalent compressive properties of the CFR - SP - PEEK / HA composite material obtained through compression testing and numerical simulation are as shown in Figure 12(As shown in (a) - (b)), it can be seen that the CFR - SP - PEEK / HA composite material exhibits elastic - brittle properties when subjected to compressive loads. When the ultimate load is reached, its load - bearing capacity drops rapidly. The test values, theoretical values, and simulation values of the equivalent compressive modulus of the CFR - SP - PEEK / HA composite material are in good agreement, with a maximum error not exceeding 4%. This indicates that the classical laminate theory and numerical simulation methods can accurately predict the equivalent compressive modulus of the CFR - SP - PEEK / HA composite material composed of CF / PEEK prepreg single - layers with different ply directions, PEEK films, and PEEK / HA - S single - layers. The error of the equivalent compressive strength value of the CFR - SP - PEEK / HA composite material obtained through the Hill - Tsai strength theory, numerical simulation, and compression test is within 5%. Therefore, it is considered that the compressive strength and elastic modulus of the CFR - SP - PEEK / HA composite material can be accurately predicted through numerical simulation and theoretical models. Through Figure 12 (c), it can be known that the failure sequence of the CFR - SP - PEEK / HA composite material under compressive loads is that after the fiber compression failure of the 0℃F / PEEK single - layer, the load - bearing capacity of the composite material drops sharply, and the compressive strain at this time is 1.13%. The remaining layers do not fail, which is Figure 7 (b) The predicted failure sequence is basically the same.

[0108] By taking SEM images of the compression side and cross - section of the CFR - SP - PEEK / HA composite material, as Figure 13 shown, cracking between the composite materials is observed, and some positions are broken into multiple segments. By magnifying and scanning the tensile cross - section, as the magnification increases, it is observed that the fibers and matrix of the 0℃F / PEEK single - layer undergo compressive fracture, and the carbon fiber filaments are broken into two or even three segments. However, the interface between the CF / PEEK single - layer and PEEK / HA - S does not fail, indicating good interface performance between them, which is basically the same as the failure mode predicted in the theoretical model and numerical simulation.

[0109] In summary, the embodiments of this application conduct mechanical property tests on the CFR - SP - PEEK / HA composite material, and further analyze its mechanical response and internal failure mechanism through theoretical models and numerical simulations. The numerical simulation, theoretical model, and experimental results are in good agreement. It is proved that the CFR - SP - PEEK / HA composite material shows great potential in the field of artificial bone repair.

[0110] Example 4

[0111] The embodiments of this application provide an implant, and the preparation material of the implant includes the novel carbon fiber - reinforced surface - porous composite material as described in Example 1.

[0112] In the late stage of fracture recovery, insufficient mechanical stimulation of bone tissue leads to symptoms such as osteoporosis. After the removal of the steel plate, it is often prone to break again. Generally, the longer the fixation time, the worse the mechanical properties of the bone. In the bone, osteoblasts and osteoclasts in bone tissue regulate bone growth or absorption by sensing mechanical stimulation. When stress shielding occurs in bone tissue, the stress level on the bone tissue often remains at a low level for a long time, causing the bone tissue to be gradually absorbed by the human body, resulting in osteoporosis at the fracture site. After recognizing the stress shielding mechanism, great improvements have been made in fracture fixation methods. Using composite material bone plates with stiffness matching that of the implanted bone to give more mechanical stimulation to bone tissue during the rehabilitation process. Therefore, the problem of composite materials that can match the mechanical properties of bones in different positions has become an urgent problem to be solved. In the embodiment of this application, taking the matching of the mechanical properties of the human femur as an example, a CFR-SP-PEEK / HA composite material with mechanical properties matching those of the human femur is designed through layup. First, determine the elastic modulus and ultimate strength of the human femur. The tensile modulus of the human femur is 18.43 GPa, and the tensile strength is 133 MPa; the compression modulus is 17.9 GPa, and the compression strength is 137 MPa; the bending modulus is 18.33 GPa, and the bending strength is 189 MPa. By changing the layup order of PEEK films and CF / PEEK prepregs to change the mechanical properties of the CFR-SP-PEEK / HA composite material to match the mechanical properties of the human femur.

[0113] In one implementation, as can be seen from Table 1, the elastic modulus of the CF / PEEK single plate in the 1 direction is much greater than that in the 2 and 3 directions, and there is no order-of-magnitude difference between the elastic moduli in the 2 / 3 directions and those of the PEEK film and PEEK / HA-S. Therefore, the in-plane effective modulus of the CFR-SP-PEEK / HA composite material in the 1 direction is mainly determined by the relative thickness of the 0°C F / PEEK single plate and the relative thickness of the PEEK / HA-S. Assuming that the total number of layers of the PEEK film and the CF / PEEK single plate is 11 and the number of layers of the 90°C F / PEEK single plate is 0, calculate the in-plane effective moduli of the composite material in the 1 and 2 directions. The results are as Figure 14(a) and (b). The in-plane effective modulus of the CFR-SP-PEEK / HA composite in the 1 direction is mainly determined by the relative thickness of the 0°C F / PEEK veneer and the relative thickness of the PEEK / HA-S. Compared with the relative thickness of the PEEK / HA-S, the in-plane effective modulus in the 1 direction is more sensitive to the change in the relative thickness of the 0°C F / PEEK veneer. When the relative thickness of the PEEK / HA-S is between 0.477 and 0.563 and the relative thickness of the 0°C F / PEEK veneer is between 0.040 and 0.517, the in-plane effective modulus in the 1 direction is between 7.84 and 68.12 GPa, and this basic range covers the mechanical properties of cortical bone from 3 to 35 GPa. Therefore, by changing the ply stacking method of the prepreg and the relative thickness of the PEEK / HA-S, its mechanical properties can be changed, which is beneficial to reducing the stress shielding caused by bone resorption. This characteristic is considered to improve the in-vivo function of the implant.

[0114] In one embodiment, by Figure 14 (b), it can be seen that when the relative thickness of the PEEK / HA-S is between 0.477 and 0.563 and the relative thickness of the 0°C F / PEEK is between 0.040 and 0.517, the in-plane effective elastic modulus in the 2 direction is between 3.46 and 6.41 GPa, and the change range of its elastic modulus is not large. This is because the elastic modulus of the 90°C F / PEEK veneer is not much different from the moduli of the PEEK film and the PEEK / HA-S. Calculate the tensile and compressive strengths of the CFR-SP-PEEK / HA composite in the 1 direction as Figure 14 (c) and (d) show. When the relative thickness of the PEEK / HA-S is between 0.477 and 0.563 and the relative thickness of the 0°C F / PEEK is between 0.040 and 0.517, the tensile and compressive strengths of the CFR-SP-PEEK / HA composite are between 116.14 and 1170.67 MPa and between 87.53 and 774.08 MPa, respectively. Compared with the relative thickness of the PEEK / HA-S veneer, the tensile and compressive strengths of the CFR-SP-PEEK / HA composite are more sensitive to the change in the relative thickness of the 0°C F / PEEK.

[0115] According to Figure 14As shown, when the number of 0°F / PEEK prepreg layers is 3 and the thickness is 3.90 mm, the relative thickness of 0°F / PEEK is 11.92%. The in-plane effective modulus of CFR-SP-PEEK / HA composite in the 1 direction is 17.86 GPa, which is not much different from the tensile modulus of human femur (18.43 GPa) (error 3.1%). To balance the in-plane effective moduli of the composite in the 1 and 2 directions, when the relative thicknesses of the 90°F / PEEK single ply and the PEEK single ply are the same and other parameters remain unchanged, the in-plane effective modulus of CFR-SP-PEEK / HA composite in the 1 direction is 19.10 GPa, which is basically the same as the tensile modulus of human femur (18.43 GPa), with an error of only 3.6%. At this time, the tensile strength of the composite is 243.55 MPa, which is 83% higher than the tensile strength of human femur; the compressive strength is 213.77 MPa, which is 56% higher than the compressive strength of human femur. Based on the above conclusions, the relative thickness of different laminated single plies has a great influence on the tensile and compressive properties of the composite, while the influence of the ply sequence is smaller in symmetric layup.

[0116] In one embodiment, the equivalent flexural strength and modulus of CFR-SP-PEEK / HA composite are not only related to the relative thickness and direction of the laminated single plies, but also the relative cross-sectional position of the single plies has a great influence on its flexural properties. Based on the above conclusions of tension and compression, in order to maximize the flexural stiffness of the composite and explore the influence of the relative thickness of PEEK / HA-S single ply on the flexural modulus of CFR-SP-PEEK / HA composite, it is assumed that the composite is completely composed of PEEK / HA-S single ply, PEEK film and 0°F / PEEK. To meet the requirements of the tensile and compressive properties of the composite, when the number of 0°F / PEEK layers is preset to 2 and the total thickness is 2.6 mm, the relative thickness of 0°F / PEEK is 11.92%. The 2 layers of 0°CF / PEEK are arranged on the outermost layer by symmetric layup, and the flexural modulus of the composite is changed by changing the relative thickness of PEEK / HA-S. The specific calculation results are as Figure 15 shown. The increase in the relative thickness of PEEK / HA-S will reduce the effective flexural modulus of the composite, and they show a non-linear relationship, specifically satisfying the following functional relationship: y = 55.10e -x / 36.8 -3.39 and its correlation coefficient can reach 99.92%.

[0117] When the relative thicknesses of the 0℃F / PEEK single board and the PEEK / HA-S single board are 11.92% and 33.88% respectively, the flexural modulus of the CFR-SP-PEEK / HA composite material can reach 18.85 GPa. The specific layup sequence is PEEK / HA-S(0.4385mm) / 0 / P / P / P / P / P / P / P / P / P / 0 / PEEK / HA-S(0.4385mm).

[0118] In one embodiment, by replacing two layers of PEEK films near the neutral axis position with 90℃F / PEEK, the mechanical properties of the composite material in the x-axis and y-axis directions can be balanced without almost changing the flexural modulus of the composite material. The specific layup is PEEK / HA-S(0.4405mm) / 0 / P / P / P / 90 / P / 90 / P / P / P / 0 / PEEK / HA-S(0.4405mm). At this time, the equivalent flexural modulus of the composite material is 18.79 GPa, which is basically the same as the flexural modulus of the human femur, 18.33 GPa, and the error is only 2.5%.

[0119] In one embodiment, in order to increase the flexural strength at the first yield point of the CFR-SP-PEEK / HA composite material without changing the flexural modulus of the composite material, the relative thickness of PEEK / HA-S is changed to achieve the downward movement of the neutral axis on the premise that the rest of the layup remains unchanged, which is beneficial to the reasonable distribution of stress. The specific layup method from bottom to top is PEEK / HA-S(7.0%) / 0 / P / P / P / 90 / P / 90 / P / P / P / 0 / PEEK / HA-S(26.9%). This layup method changes the relative position of the neutral axis and has little impact on the absolute position of the neutral axis. At this time, the equivalent flexural modulus of the composite material is 18.93 GPa, which is basically the same as the flexural modulus of the human femur, 18.33 GPa, and the error is only 3.2%.

[0120] In the above embodiments, the mechanical properties of the CFR-SP-PEEK / HA composite material are personalized designed to match the biomechanical properties of the human femur, so that its mechanical properties can fully match the tensile, compressive and flexural properties of the human femur. In order to prove the designability of the above method for the mechanical properties of bones in various parts of the human body, the CFR-SP-PEEK / HA composite material is personalized designed below to meet the matching of the biomechanical properties of the human tibia. First, determine the biomechanical properties of the human tibia, including its tensile, compressive and flexural properties.

[0121] In one embodiment, the tensile strength and modulus of the human tibia are 156.4 MPa and 24.2 GPa, respectively; the compressive strength and modulus are 191.8 MPa and 26.5 GPa, respectively; the flexural strength and modulus are 197.0 MPa and 18.9 GPa, respectively. Since the tensile and compressive properties of the CFR-SP-PEEK / HA composite are mainly determined by the relative thickness of the 0°F / PEEK single board, and the tensile and compressive moduli of the CF / PEEK single board are the same, the target values of the tensile and compressive moduli of the composite are designed to be the average of the tensile and compressive moduli of the human tibia, that is, 25.35 GPa. According to Figure 14 It can be seen that when the relative thicknesses of PEEK / HA-S, PEEK, 0° and 90°F / PEEK are 52.3%, 30.5%, 17.2% and 0%, respectively, the tensile and compressive moduli of CFR-SP-PEEK / HA are 24.6 GPa, and the tensile strength and compressive strength are 407.6 MPa and 278.6 MPa, respectively. Therefore, it is assumed that the number of 0°F / PEEK layers is 4 and the total thickness is 3.6 mm. The 0°F / PEEK is arranged tightly inside the PEEK / HA-S single board. When the relative thicknesses of the PEEK / HA-S single board, PEEK film, 0° and 90°F / PEEK single board are 39.4%, 26.2%, 17.2% and 17.2%, respectively, and the layup sequence from bottom to top is PEEK / HA-S(6.1%) / 0 / 0 / 90 / 90 / P / P / P / P / P / P / 90 / 90 / 0 / 0 / PEEK / HA-S(33.3%). According to the calculation of the theoretical model, the mechanical properties of the CFR-SP-PEEK / HA composite obtained by layup in the above manner can be perfectly matched with the human tibia, and the maximum error is only 8%. Based on the above conclusions and calculation methods, by adjusting the layup direction and relative thickness of PEEK, CF / PEEK single board and PEEK / HA-S, the mechanical properties of the CFR-SP-PEEK / HA composite can be changed to match the biomechanical properties of bones in different positions of the human body, realizing personalized customization of bones in different parts of different individuals. And due to the anisotropy of the CFR-SP-PEEK / H composite, it can well match the mechanical properties of bones with different tensile, compressive and flexural moduli.

[0122] In summary, the mechanical behavior of the implant CFR-SP-PEEK / HA composite proposed in the embodiment of the present application can be matched with human cortical bone by adjusting the layup process parameters. At the same time, the surface of the sample shows potential ultra-high bioactivity and has excellent potential in bone implantation.

[0123] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but rather should be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0124] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.

Claims

1. A novel carbon fiber reinforced surface porous composite material, characterized in that, Including: Two functionalized porous structures, a number of carbon fiber polyether ether ketone prepregs, and a number of polyether ether ketone films. Each carbon fiber polyether ether ketone prepreg and each polyether ether ketone film are alternately laid between the two functionalized porous structures according to a preset layering sequence; The functionalized porous structure is a polyether ether ketone mixture after hot pressing. The carbon fiber polyether ether ketone prepreg is a first carbon fiber polyether ether ketone prepreg with a laying direction of 0° or a second carbon fiber polyether ether ketone prepreg with a laying direction of 90°; The surface porous composite material includes 4 layers of polyether ether ketone films and 7 layers of carbon fiber polyether ether ketone prepregs; The preset layering sequence of the 4 layers of polyether ether ketone films and 7 layers of carbon fiber polyether ether ketone prepregs is as follows: polyether ether ketone film, first carbon fiber polyether ether ketone prepreg, second carbon fiber polyether ether ketone prepreg, polyether ether ketone film, first carbon fiber polyether ether ketone prepreg, second carbon fiber polyether ether ketone prepreg, first carbon fiber polyether ether ketone prepreg, polyether ether ketone film, second carbon fiber polyether ether ketone prepreg, first carbon fiber polyether ether ketone prepreg, polyether ether ketone film; A preparation method for preparing the novel carbon fiber-reinforced surface porous composite material includes: Using a three-dimensional weaving method to weave aluminum wires into a 3D aluminum scaffold, filling the polyether ether ketone mixed powder into the 3D aluminum scaffold and performing hot pressing to obtain a composite material 3D aluminum scaffold; Placing the composite material 3D aluminum scaffold at the bottom of a hot pressing mold, alternately laying each carbon fiber polyether ether ketone prepreg and each polyether ether ketone film above the composite material 3D aluminum scaffold according to a preset layering sequence, and then placing another composite material 3D aluminum scaffold on top of the hot pressing mold; Performing hot pressing on the hot pressing mold, and when the hot pressing mold cools to room temperature, opening the mold and taking out the specimen; By means of cutting and etching solution methods, milling off the polymers coating the 3D aluminum scaffold in the composite material 3D aluminum scaffolds on the upper and lower surfaces of the specimen to obtain the surface porous composite material.

2. The surface porous composite material according to claim 1, characterized in that, The pore diameter of the functionalized porous structure is 0.6 mm, the thickness of the carbon fiber polyether ether ketone prepreg is 0.155 mm, and the thickness of the polyether ether ketone film is 0.157 mm.

3. The surface porous composite material according to any one of claims 1 or 2, characterized in that The polyether ether ketone mixture includes: polyether ether ketone and a bioactive material. Among them, the bioactive material is any one of hydroxyapatite, calcium phosphate ceramics, bioactive glass, zirconia, silicon nitride, and aluminate ceramics.

4. The surface porous composite material according to any one of claims 1 or 2, characterized in that, The polyether ether ketone mixture includes: polyether ether ketone and a catalyst material. Among them, the catalyst material is any one of alumina, aluminosilicate, copper catalyst, molybdenum catalyst, and platinum group metal catalyst.

5. The surface porous composite material according to any one of claims 1 or 2, characterized in that, The polyether ether ketone mixture includes: polyether ether ketone and an adsorbent material. Among them, the adsorbent material is any one of activated carbon, zeolite, activated alumina, and titanium oxide.

6. The surface porous composite material according to any one of claims 1 or 2, wherein The polyether ether ketone mixture includes: polyether ether ketone and an insulating material. Among them, the insulating material is any one of ceramic materials, silicone rubber, glass fiber, ceramic fiber, and silicone glue.

7. The surface porous composite material according to any one of claims 1 or 2, characterized in that The polyether ether ketone mixture includes: polyether ether ketone and an electromagnetic shielding material. Among them, the electromagnetic shielding material is any one of copper alloys, nickel-based alloys, conductive ceramic materials, conductive coating materials, and carbon fibers.

8. An implant, characterized in that, The preparation material of the implant includes the novel carbon fiber reinforced surface porous composite material as described in Claim 1.

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