Short carbon fiber reinforced polyether-ether-ketone composite material as well as preparation method and application thereof

Abstract

The invention relates to a short carbon fiber reinforced polyether-ether-ketone composite material as well as a preparation method and application thereof, the composite material comprises a polyether-ether-ketone matrix serving as a continuous phase and short carbon fibers serving as a reinforcing phase, and the surfaces of the short carbon fibers are provided with modified layers; the bioactive components in the modified layer comprise beta-tricalcium phosphate and aluminum-containing phosphate. The short carbon fiber reinforced polyether-ether-ketone composite material provided by the invention has good mechanical properties, biological activity and biocompatibility, and can be well matched with human skeleton modulus. Besides, the preparation method provided by the invention is simple to operate, free of damage to the strength of the fiber body, low in preparation cost, environment-friendly and suitable for industrial production, and the short carbon fiber composite material provided by the invention is also particularly suitable for 3D printing to form a final target product.

Description

Technical Field

[0002] The present invention belongs to the technical field of polyetheretherketone composite materials, and relates to a short carbon fiber reinforced polyetheretherketone composite material, its preparation method and application, specifically to a short carbon fiber reinforced polyetheretherketone composite material with bioactivity, its preparation method and application, and the short carbon fiber composite material provided by the present invention is also suitable for 3D printing. Background Art

[0004] In modern medicine, fracture repair has become one of the key directions in clinical treatment. With the aggravation of population aging and the increase in the intensity of social activities, the demand for orthopedic repair materials has shown an explosive growth. However, although the titanium alloy repair materials widely used clinically at present have advantages such as high strength and corrosion resistance, due to their elastic modulus (about 120 GPa) being much higher than that of human bone tissue (about 20 GPa), it is easy to cause the stress shielding effect, thereby inhibiting the regeneration of bone tissue. In addition, the X-ray blocking property of titanium alloy repair materials also brings difficulties to the observation and evaluation of postoperative bone healing.

[0005] Carbon fiber reinforced polyetheretherketone (CF / PEEK) composite materials are a kind of orthopedic materials with great application prospects and have become a research hotspot in recent years because of their mechanical properties close to those of bone tissue, excellent biocompatibility and low density, and at the same time, they also inherit the non-toxicity, good chemical resistance, natural ray permeability, and even magnetic resonance imaging compatibility of PEEK. However, for CF / PEEK composite materials to be used as load-bearing orthopedic materials, there are still areas that need improvement: on the one hand, because the surface of CF is smooth and cannot form an effective mechanical engagement with PEEK, and at the same time its surface shows chemical inertness and low surface energy, and cannot form a chemical bond with PEEK. These reasons together lead to poor compatibility and weak interfacial interaction between CF and PEEK. When an external load acts on the fiber-reinforced resin composite material, the interface cannot effectively transfer stress, and too much stress acts on the interface, resulting in interface cracking and the failure of the overall composite material. On the other hand, in order to effectively achieve bone regeneration and fracture healing, it is crucial to integrate the implant material with the surrounding bone tissue. However, CF / PEEK does not have bioactivity, which is not conducive to cell growth and adhesion, and its inferior osteointegration ability makes it unable to form a firm bond with human bone tissue after being implanted into the human body, thus affecting the long-term stability of the implant material in the human body. These problems seriously hinder the clinical application of CF / PEEK composite materials.

[0006] In the CF / PEEK composite material, it is mainly composed of three parts: CF as the reinforcing phase, the PEEK matrix as the continuous phase, and the interfacial phase connecting CF and PEEK. Among them, the interfacial phase is an important bridge for performance transfer between the fiber and the matrix. In the research on the interfacial modification of composite materials, improving the interfacial performance is crucial for enhancing the overall mechanical properties of composite materials. Good interfacial bonding can effectively transfer loads, thereby improving the mechanical properties such as the flexural strength and flexural modulus of composite materials.

[0007] Currently, the commonly used interfacial modification methods include carbon fiber modification and PEEK matrix modification. The modification methods for the PEEK matrix are usually dangerous and complex. For example, as cited in Reference 1 for the modification of the PEEK matrix, the preparation process of sulfonated polyether ether ketone is complex and dangerous. Modifying the surface of carbon fiber is a commonly used and efficient method. Surface modification of carbon fiber materials can, to a certain extent, improve the wettability of carbon fiber in the PEEK matrix, enhance the bonding strength between the two, and thus improve the properties of composite materials.

[0008] In Reference 2, sulfonated polyether ether ketone grafting, treatment with concentrated nitric acid at room temperature, treatment with concentrated nitric acid in a hot water bath at high temperature, ultrasonic treatment with a mixed acid (nitric acid + concentrated sulfuric acid), and polyacrylonitrile-based carbon fibers that only remove the surface oxide layer were used to prepare composite materials with PEEK. The results show that the carbon fibers after ultrasonic treatment with the mixed acid for 20 minutes have a better wetting effect, are more conducive to the preparation of composite materials, and have the best enhancement effect on the mechanical properties of the materials.

[0009] Reference 3 discloses an interfacial modification method for carbon fiber reinforced polyether ether ketone composite materials. It uses polyetherimide (PEI) and polyetherimide / graphene oxide (PEI / GO) to perform interfacial modification on the surface of carbon fibers after activation treatment with 37wt% concentrated nitric acid, and then prepares CF / PEEK composite materials by compression molding. The results show that the 1wt% PEI modifier effectively enhances the interaction force between the fiber and the matrix, and the addition of 0.5wt% GO further improves the interfacial bonding performance. The interlaminar shear strength is increased by 68%, and the flexural strength and flexural modulus are increased by 54% and 68% respectively.

[0010] Reference Document 4 discloses a method for preparing a modified carbon fiber reinforced polyetheretherketone composite material, including: 1) Immerse carbon fiber tows in an extraction solution of an organic solvent to obtain degummed carbon fibers; immerse the degummed carbon fibers in a water / p-phenylenediamine mixed solution, add isoamyl nitrite, stir, filter and rinse; 2) Disperse carbon nanoparticles in water by ultrasonic method, immerse carbon fibers in the dispersion of carbon nanoparticles, add isoamyl nitrite, stir, filter and wash; 3) Mix the raw materials of polyetheretherketone and processing aids and the modified carbon fibers in a twin-screw extruder, melt extrude and pelletize to obtain the product. This method uses a diazonium salt reaction to activate carbon fibers and load carbon nanoparticles on the surface of carbon fibers, improving the surface activity of carbon fibers and the wettability between fibers and resins; there is a good mechanical bonding force between the modified carbon fibers and PEEK resin, which can effectively improve the mechanical properties of the composite material.

[0011] Reference Document 1: CN108047470A

[0012] Reference Document 2: Wei Jiashun, Pan Lei, Tao Jie, etc. Influence of surface treatment on wettability of carbon fibers and tensile properties of continuous fiber reinforced PEEK composites [J]. Fiber Composites, 2010, 4: 36-40.

[0013] Reference Document 3: Sun Yijian, Wu Ju, Elwathig A. M. Hassan, etc. Interface modification of carbon fiber reinforced polyetheretherketone composites [J]. High-Tech Fiber & Application, 2021, 46(02): 21-27.

[0014] Reference Document 4: CN105219018A Summary of the Invention

[0016] Problems to be Solved by the Invention

[0017] As described above, although there has been prior art research on the modification of the surface of carbon fibers, most of the modified carbon fiber reinforced polyetheretherketone composite materials are treated with acid solutions (such as Reference Document 2 and Reference Document 3), and the acid solutions will damage the surface of carbon fibers, and the damaged carbon fiber surface has a great impact on the mechanical properties of the composite material.

[0018] The modification method in Reference Document 4 effectively improves the surface activity of carbon fibers and greatly improves the mechanical strength of carbon fiber composites, and does not damage the strength of the fiber body, but it cannot bring certain biological activity to the carbon fiber / polyetheretherketone composite material, so the goal of being applied to the preparation of bone repair materials cannot be achieved.

[0019] In summary, it is urgent to improve the inert surface of carbon fiber and develop a carbon fiber reinforced polyetheretherketone composite material with mechanical properties that can adapt to the growth environment required by human bones. On the other hand, it should also have certain bioactivity so that it can be applied to the human body without rejection. How to perfectly combine these two is the key to solving the problems faced by CF / PEEK composite materials in the preparation of bone repair materials.

[0020] Therefore, to solve the deficiencies in the existing technology, the purpose of the present invention is to provide a carbon fiber reinforced polyetheretherketone composite material with good interfacial bonding, bioactivity, and biocompatibility, which is non-toxic and harmless and easy to industrialize, as well as its preparation method and application. The carbon fiber reinforced polyetheretherketone composite material of the present invention overcomes the problem that CF / PEEK composite materials in the existing technology cannot simultaneously achieve good mechanical properties and bioactivity. At the same time, its preparation method is simple to operate, conducive to large-scale production and will not affect the inherent properties of carbon fiber materials. In particular, the above method of the present invention also solves the problem that CF / PEEK composite materials cannot be applied to the preparation of bone repair materials due to lack of bioactivity. In addition, the short carbon fiber composite material of the present invention is also suitable for 3D printing to prepare the final products.

[0021] Solutions for solving the problems

[0022] It has been found that by implementing the following technical solutions, the above technical problems can be solved:

[0023] [1]. The present invention provides a short carbon fiber reinforced polyetheretherketone composite material, wherein the composite material includes a polyetheretherketone matrix as the continuous phase and short carbon fibers as the reinforcing phase, and a modified layer is present on the surface of the short carbon fibers;

[0024] The bioactive components in the modified layer include β-tricalcium phosphate and aluminum-containing phosphate.

[0025] [2]. The composite material according to [1], wherein, based on the total mass of the composite material, the content of the short carbon fibers as the reinforcing phase is 10-30 wt%.

[0026] [3]. The composite material according to [1] or [2], wherein the short carbon fibers in the composite material are non-oriented or oriented along any one axis direction.

[0027] [4]. The composite material according to [1] or [2], wherein the length of the short carbon fibers is 10-500 μm.

[0028] [5]. The composite material according to [1] or [2], wherein the aluminum phosphate-containing material includes one or both of calcium aluminum phosphate and aluminum phosphate; the modified layer is obtained by electrodeposition from an electrolyte solution containing a calcium source and a phosphorus source, and in the electrolyte solution, the molar ratio of calcium to phosphorus is greater than 1:1 and less than 1.5:1; the thickness of the modified layer is below 1 μm.

[0029] [6]. The present invention also provides a method for preparing a short carbon fiber reinforced polyetheretherketone composite material according to any one of [1]-[5], wherein the preparation method includes the following steps:

[0030] 1) The step of surface modification of short carbon fibers: Using an acidic solution containing a calcium source and a phosphorus source as the electrolyte, and using an aluminum sheet as the anode and cathode, perform electrodeposition on the short carbon fibers, and then perform anaerobic sintering to obtain short carbon fiber powder with a modified layer on the surface; before the electrodeposition, the short carbon fibers have been subjected to plasma oxidation treatment;

[0031] 2) The mixing step: Use a solvent to uniformly mix the short carbon fiber powder with a modified layer on the surface and the polyetheretherketone powder, perform suction filtration, and dry to obtain a mixed powder;

[0032] 3) The step of molding by compression: Mold the mixed powder by compression to obtain a short carbon fiber reinforced polyetheretherketone composite material.

[0033] [7]. The preparation method according to [6], wherein in step 1),

[0034] the pH value of the electrolyte solution is 3-5;

[0035] the molar ratio of calcium to phosphorus in the electrolyte solution is greater than 1:1 and less than 1.5:1.

[0036] [8]. The preparation method according to [6] or [7], wherein in step 1),

[0037] the conditions of the plasma oxidation treatment include: the power is 5-50 W, the time is 10 s-5 min, and the gas source is any one of oxygen, argon, nitrogen, and air.

[0038] [9]. The preparation method according to [6] or [7], wherein in step 2),

[0039] the solvent is alcohol;

[0040] the mass ratio of the short carbon fiber powder with a modified layer on the surface to the polyetheretherketone powder is 1:(3-5).

[0041]

[10] . Further, the present invention also provides an application of the short carbon fiber reinforced polyetheretherketone composite material according to any one of [1]-[5], or the short carbon fiber reinforced polyetheretherketone composite material prepared by the preparation method according to any one of [6]-[9] in the preparation of bone repair materials.

[0042] Effects of the Invention

[0043] Based on the implementation of the above technical solutions, the present invention can obtain the following technical effects:

[0044] In the short carbon fiber reinforced polyetheretherketone composite material prepared by the present invention, there are intermolecular forces such as hydrogen bonds and van der Waals forces generated between the carbon fibers and the polyetheretherketone matrix, which are more strongly combined with the polyetheretherketone matrix and not easily fall off. Moreover, there are also hydrogen bonds generated between the carbon fibers and the bioactive components (β-tricalcium phosphate and aluminum-containing phosphate) in the modified layer. A short carbon fiber reinforced polyetheretherketone composite material with uniform order, excellent mechanical properties, bioactivity and biocompatibility is obtained, which can well match the modulus of human bones and better meet the requirements of contemporary orthopedic medical applications, and is expected to be applied to the field of load-bearing orthopedics.

[0045] The preparation method of the present invention effectively improves the bioactivity on the surface of carbon fibers and greatly improves the mechanical properties of the carbon fiber reinforced polyetheretherketone composite material, and will not cause damage to the strength of the fiber body. The preparation cost is low, environmentally friendly, and suitable for industrial production.

[0046] The short carbon fiber composite material of the present invention is also applicable to the preparation of various final products by 3D printing, so it has extremely high degrees of freedom in use and forming. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 It is the process flow chart of the preparation of the short carbon fiber reinforced polyetheretherketone composite material of the present invention;

[0049] Figure 2 It is the optical microscope diagram of the short carbon fibers before and after modification of the present invention;

[0050] Figure 3 It is the SEM diagram of the short carbon fibers before and after modification of the present invention;

[0051] Figure 4 It is the enlarged SEM diagram of the modified short carbon fiber ECF20 in Example 1 of the present invention;

[0052] Figure 5 It is the EDS elemental analysis diagram of the surface of the modified short carbon fiber ECF20 in Example 1 of the present invention;

[0053] Figure 6X-ray diffraction pattern of the inorganic non-metallic material coating in Example 1 of the present invention;

[0054] Figure 7 Phase composition diagram of the inorganic non-metallic material coating in Example 1 of the present invention;

[0055] Figure 8 Graph showing the results of static contact angle tests of short carbon fibers before and after modification of the present invention;

[0056] Figure 9 Graph showing the results of surface energy tests of short carbon fibers before and after modification of the present invention;

[0057] Figure 10 Graph showing the results of flexural strength tests of short carbon fiber reinforced polyetheretherketone composites prepared in each example and comparative example of the present invention;

[0058] Figure 11 Graph showing the results of flexural modulus tests of short carbon fiber reinforced polyetheretherketone composites prepared in each example and comparative example of the present invention;

[0059] Figure 12 Comparative diagram of cross-sectional SEM morphologies of short carbon fiber reinforced polyetheretherketone composites prepared in each example and comparative example of the present invention;

[0060] Figure 13 Magnified comparative diagram of cross-sectional SEM morphologies of short carbon fiber reinforced polyetheretherketone composites prepared in each example and comparative example of the present invention. Detailed implementation manners

[0062] The following describes the implementation manners of the present invention, but the present invention is not limited thereto. The present invention is not limited to the various components described below. Various modifications can be made within the scope claimed for the invention, and implementation manners and examples obtained by appropriately combining the technical means disclosed in different implementation manners and examples are also included in the technical scope of the present invention. In addition, all the documents cited in this specification are incorporated herein by reference.

[0063] Unless otherwise defined, the technical and scientific terms used in the present invention have the same meanings as those commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0064] In this specification, the numerical range expressed by "numerical value A~numerical value B" means a range including the end point numerical values A and B.

[0065] Unless otherwise required in the present application, throughout the specification and the claims that follow, the word "comprising" shall be construed in an open, inclusive sense, i.e., "including but not limited to".

[0066] In this specification, unless otherwise specified, the "many", "multiple", "several" in "many", "multiple kinds", "several" means a numerical value of 2 or more.

[0067] In this specification, the "substantially" or "essentially" means that the error is less than 1%, or less than 0.8% or less than 0.6% compared with the relevant perfect standard or theoretical standard. In addition, when "all" or "all of" is mentioned in this specification, its meaning also refers to "substantially" or "essentially" "all" or "all of".

[0068] In this specification, unless otherwise specified, "%" all represents mass percentage content.

[0069] In this specification, the meaning expressed by using "can" includes the meanings of both performing a certain treatment and not performing a certain treatment.

[0070] In this specification, "optional" or "optionally" means that the subsequent described event or situation may or may not occur, and this description includes the situation where the event occurs and the situation where the event does not occur.

[0071] In this specification, the "some specific / preferred embodiments", "some other specific / preferred embodiments", "embodiments", etc. mentioned refer to the specific elements (such as features, structures, properties, and / or characteristics) related to the embodiment, which are included in at least one of the embodiments described herein, and may or may not exist in other embodiments. In addition, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0072] In this specification, when using "normal temperature" or "room temperature", the temperature can be 23±2°C.

[0073] The first aspect

[0074] The first aspect of the present invention provides a short carbon fiber reinforced polyetheretherketone composite material, especially a short carbon fiber reinforced polyetheretherketone composite material with bioactivity. Among them, the composite material includes a polyetheretherketone matrix as the continuous phase and short carbon fibers as the reinforcing phase, and a modified layer is present on the surface of the short carbon fibers.

[0075] (Polyetheretherketone)

[0076] Polyetheretherketone (PEEK) is a member of the polyaryletherketone family. It consists of an aromatic molecular backbone, ketone and ether functional groups between aromatic rings. The strong benzene rings, flexible ethers and carbonyl groups that can enhance intermolecular attraction form the molecular structure of PEEK. This chemical structure endows PEEK with the following excellent properties: 1) Heat resistance: The glass transition temperature of PEEK is 143°C, and the melting temperature is 334°C. Carbon fiber reinforced polyetheretherketone composites can be used at 260°C, and its heat distortion temperature is as high as 300°C; 2) Wear resistance: The excellent wear resistance of PEEK can be comparable to that of polyimide; 3) Flame retardancy: Only a small amount of smoke and toxic gases are generated during combustion; 4) Hydrolysis resistance: PEEK can be used in hot water or steam environments at 300°C; 5) Chemical resistance: PEEK has high tolerance to many chemicals; 6) Biocompatibility: The biocompatibility of PEEK is close to that of titanium alloy, and it is widely used as internal implants for spinal surgery, joint surgery, trauma surgery and bone defect repair.

[0077] (Short carbon fiber)

[0078] Short carbon fiber is a fiber material composed of carbon elements. It has excellent properties such as high strength, high modulus, high temperature resistance, corrosion resistance and low density, and is widely used in the field of composite materials such as reinforced resins.

[0079] In the present invention, the size of the short carbon fiber is not particularly limited in principle. It can be obtained by self-making or commercially purchased. In some preferred embodiments, the particle size of the short carbon fiber is 10 - 500 μm, preferably 10 - 120 μm, and the fiber diameter of the short carbon fiber is 0.1 - 10 μm. Therefore, it can be understood that the carbon fiber has a micron-scale size in the particle size (length or particle size) direction and a nano-to-micron size in the (cross-section) diameter of the fiber.

[0080] Furthermore, as a description of the particle size of the short carbon fiber, it is not limited to the length of fine single fiber particles. It goes without saying that the particle size of the short carbon fiber described above in the present invention should be understood as the maximum size of independent fiber particles (which can be single fibers or aggregates of several fibers). For example, when the short carbon fiber is a single fiber, the particle size refers to the length of the single fiber; when the short carbon fiber is a fiber sheet, the particle size refers to the maximum size of the fiber sheet; when the short carbon fiber is a spherical fiber mass, the particle size is the diameter of the fiber mass.

[0081] In some specific embodiments, the short carbon fibers in the composite material are non-oriented or oriented along any one of the axial directions. Specifically, when the orientation of the short carbon fibers in the composite material is non-oriented, that is, the fibers are randomly distributed without a specific directionality, this random distribution helps the material to have relatively uniform mechanical properties in all directions; however, in some cases, the short carbon fibers can also be processed to be oriented along a specific direction. For example, after the composite material is formed, mechanical stretching can make the fibers oriented to a certain extent along the stretching direction, and the oriented fibers can significantly improve the strength and stiffness of the material in a specific direction. Therefore, the orientation method of the short carbon fibers needs to be designed and controlled according to specific application requirements.

[0082] In some specific embodiments, based on the total mass of the composite material, the content of the short carbon fibers as the reinforcing phase is 10-30 wt%, preferably 15-25 wt%, and can be, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, etc.

[0083] In some specific embodiments, for the modified layer of the present invention, its thickness is less than 1 μm, preferably less than 800 nm, more preferably less than 600 nm, further preferably 100-600 nm, and more preferably 300-600 nm.

[0084] In some specific embodiments, the modified layer is obtained by electrodeposition from an electrolyte containing a calcium source and a phosphorus source, and in the electrolyte, the molar ratio of calcium to phosphorus is greater than 1:1 and less than 1.5:1.

[0085] In some specific embodiments, the bioactive components in the modified layer include β-tricalcium phosphate and aluminum-containing phosphate.

[0086] In some preferred embodiments, the aluminum-containing phosphate includes one or two of calcium aluminum phosphate and aluminum phosphate.

[0087] (β-tricalcium phosphate)

[0088] β-Tricalcium Phosphate (β-TCP) is a bioceramic material with the chemical formula Ca3(PO4)2 and a calcium-to-phosphorus atomic ratio of 1.5. It is a crystal form of calcium phosphate and has the following excellent properties: 1) Biocompatibility: Compatible with human tissues and suitable for biomedical applications; 2) Biodegradability: Can be gradually degraded in the body and replaced by new bone; 3) Osteoconductivity: Promotes new bone growth; 4) Mechanical properties: Has certain mechanical strength and is suitable for load-bearing parts. Such materials are widely used in biomedical fields such as bone repair. After implantation into the body, they directly fuse with the bone without any local inflammatory reaction or systemic toxic side effects.

[0089] (Calcium aluminum phosphate)

[0090] Calcium aluminum phosphate is an important inorganic compound, usually referring to a composite phosphate material containing calcium (Ca), aluminum (Al), phosphorus (P), and oxygen (O). Its chemical composition can be expressed as Ca x Al y (PO4) z , and the specific structure may vary depending on the ratios of calcium, aluminum, and phosphorus. It has the following excellent properties: 1) Biocompatibility: Calcium aluminum phosphate materials have good compatibility with human tissues and are commonly used in bone repair and dental materials; 2) Bioactivity: Can form chemical bonds with bone tissue and promote bone regeneration; 3) Thermal stability: Calcium aluminum phosphate exhibits good stability at high temperatures; 4) Mechanical properties: By adjusting the aluminum content, the hardness, strength, and wear resistance of the material can be improved. Such materials have extensive applications in biomedical fields such as bone repair and are particularly widely studied due to their biocompatibility and bioactivity.

[0091] (Aluminum phosphate)

[0092] Aluminum Phosphate (chemical formula: AlPO4) is an important inorganic compound composed of aluminum (Al), phosphorus (P), and oxygen (O). It has good biocompatibility and is widely used in biomedical fields such as bone repair. Some studies have shown that the bioactivity of aluminum phosphate is limited, but by compounding with bioactive materials such as β-TCP and calcium aluminum phosphate, its bioactivity can be significantly enhanced, making it have potential application value in the field of bone repair.

[0093] The short carbon fiber-reinforced polyetheretherketone composite material described in the present invention has good bioactivity and biocompatibility. When used as a human tissue repair material, especially a bone repair material, it can better promote the healing or repair of human tissues without the worry of producing adverse effects.

[0094] Second aspect

[0095] The second aspect of the present invention provides a method for preparing the short carbon fiber reinforced polyetheretherketone composite material described in the first aspect of the present invention. Wherein, the preparation method includes the following steps:

[0096] 1) Step of surface modification of short carbon fibers: Using an acidic solution containing a calcium source and a phosphorus source as the electrolyte, and using an aluminum sheet as the anode and cathode, electro-deposit the short carbon fibers, and then perform anaerobic sintering to obtain short carbon fiber powder with a modified layer on the surface; before the electro-deposition, the short carbon fibers have been treated by plasma oxidation;

[0097] 2) Mixing step: Use a solvent to uniformly mix the short carbon fiber powder with a modified layer on the surface and polyetheretherketone powder, perform suction filtration, and dry to obtain a mixed powder;

[0098] 3) Molding step: Mold the mixed powder to obtain a short carbon fiber reinforced polyetheretherketone composite material.

[0099] In some specific embodiments of the present invention, before the step of surface modification of the short carbon fibers, an optional step of pre-treating the short carbon fibers is further included.

[0100] (Pre-treatment of short carbon fiber powder)

[0101] The main purpose of pre-treating the short carbon fiber powder is to remove the slurry on the surface of the short carbon fiber powder, which is beneficial for subsequent surface oxidation treatment.

[0102] Specifically, the pre-treatment step of the short carbon fiber powder includes: placing a certain amount of short carbon fiber powder in acetone and stirring to wash away the surface slurry.

[0103] In some specific embodiments of the present invention, the pre-treatment conditions of the short carbon fiber powder include: the temperature can be 10~40°C, preferably 15~30°C, the rotation speed can be 100~800 rpm, preferably 200~600 rpm, and the time can be 0.5~48 h, preferably 1~24 h.

[0104] Furthermore, perform suction filtration and drying on the washed short carbon fiber powder to remove the residual acetone, and it can be taken out for use.

[0105] In some specific embodiments of the present invention, there are no special restrictions on the drying conditions. For example, the drying temperature can be 40~180°C, preferably 60~150°C; the drying time can be 0.5~48 h, preferably 1~24 h.

[0106] In addition, in order to improve the interfacial properties between carbon fibers and matrix resins, the surfaces of carbon fibers are usually oxidized industrially to endow the surfaces of carbon fibers with active oxygen-containing functional groups such as hydroxyl groups and carbonyl groups. Common methods include anodic oxidation, nitric acid oxidation, potassium permanganate oxidation, etc. However, these methods are likely to damage the surfaces of carbon fibers and destroy their mechanical properties. Therefore, in order not to damage the fiber surfaces and improve the interfacial properties between carbon fibers and matrix resins (especially polyether ether ketone), the present invention uses plasma oxidation to oxidize the surfaces of carbon fibers, making the fiber surfaces rich in various active functional groups.

[0107] (Steps of plasma oxidation treatment)

[0108] In the steps of plasma oxidation treatment of the present invention, the surface of the short carbon fibers is subjected to plasma oxidation treatment to facilitate the subsequent attachment of a modification layer on its surface. Preferably, the modification layer is an inorganic non-metallic material coating.

[0109] For the polar groups that can be selected in the steps of plasma oxidation treatment of the present invention, one or more of polar oxygen-containing functional groups such as carbonyl groups and hydroxyl groups can be listed.

[0110] In some specific embodiments of the present invention, the surface of the short carbon fibers is subjected to plasma oxidation treatment at a power of 5-50 W for 10 s-5 min until a surface with oxygen-containing functional groups is formed, and oxidized short carbon fibers are obtained.

[0111] Furthermore, in some specific embodiments of the present invention, the gas source for the plasma oxidation treatment is any one of oxygen, argon, nitrogen, and air, and oxygen is preferred.

[0112] It should be noted that the above steps of plasma oxidation treatment are only for introducing more polar groups to facilitate the activity during the subsequent combination of the modification layer. For example, in the above oxidation treatment, certain active groups can be imparted to the surface of the carbon fibers. Therefore, such treatment only improves the energy or energy level of the carbon fiber surface by introducing specific active groups, rather than forming a complete hydrophilic modification layer. Also, therefore, the above steps of plasma oxidation treatment of the present invention are not sufficient to cause losses in the properties (especially mechanical properties) of the carbon fiber material itself.

[0113] (Steps of electrodeposition)

[0114] In the steps of electrodeposition of the present invention, an acidic solution containing a calcium source and a phosphorus source is used as the electrolyte, and an aluminum sheet is used as both the anode and the cathode to perform electrodeposition on the oxidized short carbon fibers to form a precursor coating of an inorganic non-metallic material on its surface.

[0115] In some specific embodiments, the preparation of the electrolyte includes the following steps:

[0116] a). Dissolution of raw materials

[0117] The calcium source and phosphorus source are added to deionized water in a certain molar ratio, and stirred thoroughly to ensure that the calcium source and phosphorus source are completely dissolved, forming a uniform mixed solution.

[0118] b). pH adjustment

[0119] The pH value of the mixed solution is adjusted to alkaline (e.g., 8 - 10, preferably 9) by adding an alkaline solution (such as ammonia water or sodium hydroxide solution). Under alkaline conditions, calcium and phosphorus will form an insoluble precipitate (such as calcium phosphate precursor).

[0120] c). Static separation

[0121] Let it stand for a period of time to allow the precipitate to settle, and separate the supernatant and the suspension.

[0122] d). Dialysis

[0123] To remove small - molecule impurities and unreacted ions in the suspension, the suspension is filled into a dialysis bag and placed in deionized water for dialysis. Further, to improve the dialysis efficiency to ensure that impurity ions are fully removed, the deionized water used for dialysis can be changed several times during dialysis.

[0124] e). pH adjustment

[0125] After dialysis is completed, the pH value of the suspension is adjusted to acidic by adding an acidic solution. Under acidic conditions, the precipitate in the suspension will gradually dissolve, forming a clear solution, indicating that the calcium - phosphorus compound has been completely dissolved and a stable electrolyte solution has been formed.

[0126] In the present invention, for the types of calcium sources that can be used, they can be selected from water - soluble calcium salts or their hydrates. For example, they can be selected from one or more of calcium nitrate, calcium halide (except F), calcium chlorate, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate, calcium formate, calcium acetate, or their hydrates.

[0127] In the present invention, for the types of phosphorus sources that can be used, they can be selected from one or more of soluble phosphates, hydrogen phosphates, dihydrogen phosphates. For example, they can be selected from one or more of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, or phosphoric acid, etc.

[0128] In the present invention, for the types of acidic solutions that can be used, they can be selected from solutions formed by one or more of inorganic acids or organic acids. More specifically, these acidic solutions can be selected from aqueous solutions formed by one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, formic acid, acetic acid, propionic acid, etc. Among them, nitric acid is more preferably used.

[0129] In some specific embodiments of the present invention, the pH value of the electrolyte is 3 to 5, preferably 3.2 to 4.5, and for example, it can be 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, etc.

[0130] In some specific embodiments of the present invention, the molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:1, preferably 1.01:1 to 1.49:1, and for example, it can be 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.49:1, etc.

[0131] The present invention has found that during the electrodeposition process, when the current intensity is small, due to the insufficient driving force provided by the applied electric field, there are fewer crystal nucleation growth points on the surface of the carbon fiber near the cathode, and basically no coating is formed. As the current intensity increases, the crystal nuclei increase, the grain distribution on the fiber surface is uniform, and ions form a uniform inorganic non-metallic material precursor coating on the surface of the carbon fiber. When the current intensity is 10 to 30 mA, it can be found that the grains grow in a direction perpendicular to the fiber surface, and the grain size is uniform and the distribution is uniform. When the current intensity further increases, since no new nucleation points can be formed on the fiber surface, the inorganic non-metallic material begins to grow from dense growth to flower cluster-like multi-layer growth, the coating thickness increases, and even the phenomenon of coating cracking appears. The hydrogen evolution effect caused by too high current intensity is also not conducive to obtaining a uniform and dense inorganic non-metallic material precursor coating.

[0132] In some specific embodiments of the present invention, the conditions for electrodeposition include: the current intensity is 10 to 30 mA, preferably 15 to 25 mA, the electrodeposition time is 0.2 to 1 h, preferably 0.3 to 0.7 h, and the electrodeposition temperature is 40 to 60 °C, preferably 45 to 55 °C. By controlling the electrodeposition conditions within the above ranges, it is beneficial to form a uniform inorganic non-metallic material precursor coating on the surface of the carbon fiber.

[0133] (Steps of anaerobic sintering)

[0134] In the steps of anaerobic sintering of the present invention, the main purpose is to convert the inorganic non-metallic material precursor coating formed on the surface of the short carbon fiber into an inorganic non-metallic material coating through anaerobic sintering treatment.

[0135] In some specific embodiments of the present invention, the anaerobic sintering is carried out under the protection of an inert gas. For the inert gas, the present invention is not particularly limited, and it can be some gases commonly used in the art that do not participate in chemical reactions, such as nitrogen, argon, etc.

[0136] In some specific embodiments of the present invention, the conditions for oxygen-free sintering include: heating to 450-900° C. and sintering for 2-6 hours, and the heating rate is 1-10° C. / min, preferably 3-8° C. / min.

[0137] (Mixing steps)

[0138] In the mixing step of the present invention, the short carbon fiber powder having a modified layer (ie, an inorganic non-metallic material coating) on ​​the surface and the polyetheretherketone powder are uniformly mixed by using a solvent, filtered, and dried to obtain a mixed powder.

[0139] In the present invention, there is no particular limitation on the specific type of the solvent, as long as the structure and composition of the carbon fiber and polyetheretherketone are not destroyed.

[0140] In some preferred embodiments, from the perspective of easier implementation of the present invention, the solvent of the present invention is an alcohol, such as methanol, ethanol, n-propanol, isopropanol, butanol, ethylene glycol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, etc. These solvents can be used alone or in combination of two or more.

[0141] In some particularly preferred embodiments, the solvent of the present invention is anhydrous ethanol.

[0142] In some preferred embodiments, the mass ratio of the short carbon fiber powder having a modified layer on the surface to the polyetheretherketone powder is 1:(3~5), for example, it can be 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5, 1:4.8, 1:5, etc.

[0143] In the mixing step, in some preferred embodiments, from the viewpoint of better achieving the effects of the present invention, the content of the solvent is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and further preferably 80 to 90% by mass relative to the total mass of the mixed system.

[0144] In some specific embodiments, the mixing is preferably carried out under dynamic action. In the present invention, there is no particular limitation on the method for applying the dynamic action, and it can be a method known in the art, such as mechanical stirring using a high-speed stirrer, a high-speed shear emulsifier, a ball mill, a hammer mill, a vortexer, an oscillator, etc., ultrasonic irradiation, magnetic stirring, etc. In some preferred embodiments, magnetic stirring can be used.

[0145] In addition, the mixing temperature is not particularly limited in the present invention, and preferably, the mixing can be carried out at 10 to 40°C.

[0146] The drying can be carried out by various methods known in the art, for example, blowing drying, natural air drying, hot air drying in an oven, etc.

[0147] The present invention has no particular limitation on the drying conditions. For example, the drying temperature can be 40~180°C, preferably 60~150°C; the drying time can be 0.5~48h, preferably 1~24h.

[0148] (Steps of compression molding)

[0149] In the step of compression molding of the present invention, the mixed powder is compression molded to obtain a short carbon fiber reinforced polyetheretherketone composite material.

[0150] In some specific embodiments, the conditions of the compression molding include: the first stage: heating from room temperature to 300~400°C, holding for 0.1~1h, and maintaining the pressure at 2~5MPa; the second stage: cooling to 100~160°C, maintaining the pressure at 2~5MPa; the third stage: releasing the pressure and air cooling to room temperature; wherein, the heating rate is 1~10°C / min, preferably 4~8°C / min, and the cooling rate is 1~10°C / min, preferably 3~8°C / min.

[0151] The third aspect

[0152] The third aspect of the present invention provides an application of the short carbon fiber reinforced polyetheretherketone composite material according to the first aspect or the short carbon fiber reinforced polyetheretherketone composite material prepared by the preparation method according to the second aspect in the preparation of bone repair materials. In some preferred embodiments, the short carbon fiber composite material of the present invention can be used to form a repair material with a desired shape by 3D printing means.

[0153] Furthermore, for the short carbon fiber reinforced polyetheretherketone composite material constructed according to the present invention, its flexural strength is 50~300MPa, preferably 100~150MPa, and its flexural modulus is 2~30GPa, preferably 4~8GPa. Such properties can well match the modulus of human bones and are expected to be applied in the field of load-bearing orthopedics.

[0154] Examples

[0155] The embodiments of the present invention will be described in detail below in conjunction with the examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those conditions not specified in the examples, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0156] Example 1:

[0157] A preparation method of a short carbon fiber reinforced polyetheretherketone composite material, as Figure 1 shown, which comprises the following steps:

[0158] S1. Cleaning: Add a certain amount of short carbon fiber powder into acetone, stir at a speed of 400 rpm at room temperature for 10 h, filter by suction, and dry at 120 °C for 12 h to obtain clean short carbon fiber powder for standby.

[0159] S2. Plasma oxidation treatment: Place the short carbon fiber powder after the above cleaning in a plasma cleaner for plasma oxidation treatment (the gas source is oxygen, the power is 29.6 W, and the treatment time is 2 min) to obtain oxidized short carbon fiber powder.

[0160] Preparation of the electrolyte:

[0161] Add 0.656 g of calcium nitrate tetrahydrate and 0.352 g of diammonium hydrogen phosphate into 200 mL of deionized water and stir (wherein the molar ratio of calcium to phosphorus is 1:1). Adjust the pH value of the solution to 9 with ammonia water until a large amount of white precipitate precipitates. Let it stand to separate the supernatant and the suspension. Put the suspension into a dialysis bag and place it in deionized water for dialysis for 21 h, and replace the deionized water used for dialysis at the 3rd h, 6th h, and 10th h respectively. After dialysis is completed, adjust the pH value of the suspension to 3.8 with concentrated nitric acid until a clear solution is formed, that is, the electrolyte for electrodeposition is obtained.

[0162] S3. Electrodeposition: Use an aluminum sheet as the anode and cathode (wherein the cathode aluminum sheet is placed at the bottom of the beaker containing the electrolyte, and the anode aluminum sheet is placed in the upper part of the beaker containing the electrolyte). Add the oxidized short carbon fiber powder into the electrolyte. The oxidized short carbon fiber powder will spontaneously settle on the bottom cathode aluminum sheet. Electrify for 30 min under the conditions of a temperature of 50 °C and a current of 20 mA, filter, and dry at 80 °C for 12 h to obtain short carbon fiber powder with a precursor coating of inorganic non-metallic material on the surface.

[0163] Among them, the chemical reaction formula during the electrodeposition process is:

[0164]

[0165]

[0166] .

[0167] S4. Anaerobic sintering: Under argon protection, the short carbon fiber powder with an inorganic non-metallic material precursor coating on its surface is placed in a tubular furnace for anaerobic sintering treatment (heating from 50 °C to 450 °C at a rate of 5 °C / min and holding at this temperature for 1 h, then heating from 450 °C to 900 °C at a rate of 5 °C / min and holding at this temperature for 3 h, and then cooling from 900 °C to 50 °C at a rate of 5 °C / min), obtaining short carbon fiber powder with an inorganic non-metallic material coating on its surface, denoted as: ECF20.

[0168] Among them, the chemical reaction formula during anaerobic sintering is: .

[0169] S5. Powder mixing: 5 g of short carbon fiber powder with an inorganic non-metallic material coating on its surface is mixed evenly with 20 g of PEEK powder in 300 mL of absolute ethanol, filtered by suction, and dried at 120 °C for 12 h to obtain uniform mixed powder.

[0170] S6. Compression molding: The mixed powder is filled into a mold. First, use a hydraulic press to apply a pressure of 100 MPa to compact the powder, then use a pneumatic press to apply and maintain a pressure of about 3.75 MPa, heat from 25 °C to 350 °C at a rate of 6 °C / min and hold at this temperature for 20 min, cool from 350 °C to 140 °C at a rate of 5 °C / min, release the pressure, air-cool to 25 °C, demold, and use a grinding and polishing machine to polish the upper and lower surfaces at a rotational speed of 30 rpm for 5 - 15 min each to obtain a short carbon fiber reinforced polyether ether ketone composite material, denoted as: ECF20 / PEEK.

[0171] Example 2:

[0172] Compared with Example 1, the difference is that the current intensity used in electrodeposition is 30 mA.

[0173] The short carbon fiber powder with an inorganic non-metallic material coating on its surface prepared in this example is denoted as: ECF30.

[0174] The short carbon fiber reinforced polyether ether ketone composite material prepared in this example is denoted as: ECF30 / PEEK.

[0175] Comparative Example 1:

[0176] A preparation method of a short carbon fiber reinforced polyether ether ketone composite material, which includes the following steps:

[0177] S1. Cleaning: A certain amount of short carbon fiber powder is added to acetone, stirred at a rotational speed of 400 rpm at room temperature for 10 h, filtered by suction, and dried at 120 °C for 12 h to obtain clean short carbon fiber powder, denoted as: BCF.

[0178] S2. Powder mixing: Mix 5 g of the above-mentioned washed short carbon fiber powder with 20 g of PEEK powder evenly in 300 mL of absolute ethanol, perform suction filtration, and dry at 120 °C for 12 h to obtain uniform mixed powder.

[0179] S3. Compression molding: Place the mixed powder in a mold. First, use a hydraulic press to apply a pressure of 100 MPa to compact the powder, then use a pneumatic press to apply and maintain a pressure of about 3.75 MPa, heat from 25 °C to 350 °C at a rate of 6 °C / min, and keep it at this temperature for 20 min. Then cool from 350 °C to 140 °C at a rate of 5 °C / min, relieve the pressure, air-cool to 25 °C, demold, and use a grinding and polishing machine to polish the upper and lower surfaces at a speed of 30 rpm for 5 - 15 min each to obtain short carbon fiber reinforced polyether ether ketone composite material, denoted as: BCF / PEEK.

[0180] Test example:

[0181] 1. Use an optical microscope and a scanning electron microscope (SEM) to observe the changes in the surface morphology of short carbon fibers before and after modification. The optical microscope image is shown in Figure 2 , and its SEM image (magnification: 9000×) is shown in Figure 3 .

[0182] It can be seen from Figure 2 and Figure 3 that the surface of the unmodified short carbon fibers (BCF) is smooth, while the surface of the modified short carbon fibers (ECF20, ECF30) is not a smooth plane but a rough structure piled up by different particles.

[0183] It can be seen from Figure 3 that the thickness of the surface coating of the short carbon fibers after surface modification is 300 - 600 nm.

[0184] 2. The SEM image (magnification: 37400×) of the surface of the short carbon fiber powder ECF20 with an inorganic non-metallic material coating prepared in Example 1 of the present invention is shown in Figure 4 , its energy spectrum (EDS) element analysis diagram is shown in Figure 5 , its X-ray diffraction spectrum of the coating is shown in Figure 6 , and the phase composition of its coating is shown in Figure 7 .

[0185] It can be seen from Figure 4It can be seen that the surface coating of the short carbon fiber ECF20 after surface modification treatment presents a flower cluster-like morphology, and the morphology of the coating material is very similar to that of the mixture of β-tricalcium phosphate and calcium aluminum phosphate in the literature (GOLDBERG M A, SMIRNOV V V, PROTSENKO P V, etc. Influence of aluminum substitutions on phase composition and morphology of β-tricalcium phosphate nanopowders [J]. Ceramics international, 2017, 43(16): 13881-13884.).

[0186] It can be seen from Figure 5 that the main elements contained on the surface of the short carbon fiber after surface modification treatment are C, O, Ca, P, and Al elements. Since only C and O elements were contained on the surface of the short carbon fiber before modification, it can be known that Ca, P, and Al elements were successfully introduced onto the surface of the short carbon fiber after surface modification treatment.

[0187] It can be seen from Figure 6 that the positions of the main diffraction peaks of the coating material are consistent with the standard cards of Ca9Al(PO4)7 (PDF#48-1192), β-TCP (PDF#09-0169), and AlPO4 (PDF#72-1161) respectively, indicating that an inorganic non-metallic material coating was successfully prepared on the surface of the short carbon fiber.

[0188] It can be seen from Figure 7 that the inorganic non-metallic material coating is composed of 71.9 wt% calcium aluminum phosphate (chemical formula: Ca9Al(PO4)7), 5.3 wt% β-tricalcium phosphate (abbreviation: β-TCP, chemical formula: Ca3(PO4)2), and 22.8 wt% aluminum phosphate (chemical formula: AlPO4). These three substances all have excellent biocompatibility and bioactivity.

[0189] 3. The wettability of the short carbon fiber before and after modification was characterized using a contact angle measuring instrument. The standard liquids for the static contact angle test were the polar solvent deionized water (γ = 72.8 mN / m, γ d = 21.8 mN / m, γ p = 51.0 mN / m) and the non-polar solvent diiodomethane (γ = 50.8 mN / m, γ d = 50.8 mN / m, γ p = 0 mN / m). The static contact angle test results of the short carbon fiber before and after modification are shown in Table 1 and Figure 8; Based on the static contact angles between short carbon fiber samples and two liquids, the polar and non-polar components of the fibers are calculated, and finally the surface energy of the short carbon fibers is calculated. The test results are shown in Table 1 and Figure 9 .

[0190] Table 1:

[0191]

[0192] From Figure 8 and Figure 9 , it can be seen that the contact angle of the untreated short carbon fibers is the largest, indicating that the surface polarity and surface energy of the short carbon fiber material itself are both very low. The contact angles of ECF20 and ECF30 have decreased to varying degrees, and at the same time, the surface energies of ECF20 and ECF30 have increased to varying degrees, indicating that the introduction of an inorganic non-metallic material with good biocompatibility will improve the hydrophilicity and interfacial force of the short carbon fibers.

[0193] 4. According to the ASTM D790 standard, three-point bending experiments were carried out on the short carbon fiber-reinforced polyetheretherketone composites prepared in Comparative Example 1, Example 1 and Example 2. The test results of their flexural strength and flexural modulus are shown in Table 2, Figure 10 and Figure 11 as shown. Compared with BCF / PEEK, the flexural strength and flexural modulus of ECF20 / PEEK have both increased to a certain extent, by 11.65% and 1.04% respectively. Research shows that the flexural strength of cortical bone is about 50 - 300 MPa, and the flexural modulus is about 5 - 30 GPa. The flexural strength and flexural modulus of the short carbon fiber-reinforced polyetheretherketone composite prepared in the present invention are both within these ranges, and it is expected to be applied in the field of load-bearing orthopedics.

[0194] Table 2:

[0195]

[0196] 5. SEM was used to observe the cross-sectional morphology of the short carbon fiber-reinforced polyetheretherketone composites prepared in Comparative Example 1, Example 1 and Example 2. The comparison diagrams are shown in Figure 12 (magnification 50×) and Figure 13 (magnification 600×).

[0197] From Figure 12 , it can be seen that the composite material has a porous structure, and the pore size is about 200 - 400 μm. Researchers have found that compared with non-porous PEEK, porous PEEK with a pore size of 280 - 400 μm can improve bone integration while maintaining the structural integrity required for load-bearing orthopedic applications. The pore size of the short carbon fiber-reinforced polyetheretherketone composite prepared in the present invention is close to this range, and it is expected to be applied in the field of load-bearing orthopedics.

[0198] It can be seen from Figure 13 that there are more fibers pulled out from the polyether ether ketone matrix on the cross-section of the short carbon fiber reinforced polyether ether ketone composite without surface modification treatment, and the surface of the carbon fiber is smooth, and there is no polyether ether ketone attached to its surface, resulting in lower mechanical properties of the composite. No fiber pull-out phenomenon was observed on the cross-section of the surface-modified short carbon fiber reinforced polyether ether ketone composite ECF20 / PEEK, indicating that after the surface modification treatment, the surface activity of the fiber is improved, which is beneficial to the wetting between it and the polyether ether ketone matrix, and then induces the formation of transverse crystals of PEEK on its surface. When the composite is axially stressed, the transverse crystal layer plays a good role in interfacial force transfer and improves its interfacial bonding strength.

[0199] It should be noted that although the technical solutions of the present invention are introduced by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.

[0200] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of the terms used herein is intended to best explain the principles of the embodiments, the practical application or the improvement of the technology in the market, or to enable other ordinary skilled persons in the art to understand the embodiments disclosed herein.

Claims

1. A short carbon fiber reinforced polyetheretherketone composite material, characterized in that, The composite material includes a polyetheretherketone matrix as a continuous phase and short carbon fibers as a reinforcing phase, and a modified layer is present on the surface of the short carbon fibers; The bioactive components in the modified layer include β-tricalcium phosphate and aluminum-containing phosphate.

2. The composite material according to claim 1, wherein Based on the total mass of the composite material, the content of the short carbon fibers as the reinforcing phase is 10-30 wt%.

3. The composite material according to claim 1 or 2, characterized in that, The short carbon fibers in the composite material are non-oriented or oriented along any one axis direction.

4. The composite material according to claim 1 or 2, characterized in that, The length of the short carbon fibers is 10-500 μm.

5. The composite material according to claim 1 or 2, characterized in that, The aluminum-containing phosphate includes one or both of calcium aluminum phosphate and aluminum phosphate; the modified layer is obtained by electrodeposition using an electrolyte containing a calcium source and a phosphorus source, and in the electrolyte, the molar ratio of calcium to phosphorus is greater than 1:1 and less than 1.5:1; the thickness of the modified layer is 1 μm or less.

6. A method for preparing a short carbon fiber reinforced polyetheretherketone composite material according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: 1) Step of surface modification of short carbon fibers: Using an acidic solution containing a calcium source and a phosphorus source as the electrolyte, and using an aluminum sheet as the anode and cathode, electro-deposit the short carbon fibers, and then perform anaerobic sintering to obtain short carbon fiber powder with a modified layer on the surface; before the electro-deposition, the short carbon fibers have been subjected to plasma oxidation treatment; 2) Mixing step: Use a solvent to uniformly mix the short carbon fiber powder with a modified layer on the surface and the polyetheretherketone powder, perform suction filtration, and dry to obtain a mixed powder; 3) Molding step: Mold the mixed powder to obtain a short carbon fiber reinforced polyetheretherketone composite material.

7. The preparation method according to claim 6, characterized in that, In step 1), The pH value of the electrolyte is 3-5; The molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:

1.

8. The preparation method according to claim 6 or 7, characterized in that, In step 1), The conditions of the plasma oxidation treatment include: power is 5-50 W, time is 10 s-5 min, and the gas source is any one of oxygen, argon, nitrogen, and air.

9. The preparation method according to claim 6 or 7, characterized in that In step 2), The solvent is alcohol; The mass ratio of the short carbon fiber powder with a modified layer on the surface to the polyetheretherketone powder is 1:(3-5).

10. Use of the short carbon fiber reinforced polyetheretherketone composite material according to any one of claims 1-5, or the short carbon fiber reinforced polyetheretherketone composite material prepared by the preparation method according to any one of claims 6-9, in the preparation of bone repair materials.

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