Short carbon fiber reinforced polyether ether ketone composite material, preparation method and application thereof

Abstract

The present application relates to a kind of short carbon fiber reinforced polyether ether ketone composite material and its preparation method and application, the composite material includes as continuous phase polyether ether ketone matrix, as reinforcing phase short carbon fiber, and, the surface of the short carbon fiber has modification layer;The bioactive component in the modification layer includes beta-tricalcium phosphate and aluminum-containing phosphate salt.The short carbon fiber reinforced polyether ether ketone composite material provided by the present application has good mechanical properties, bioactivity and biocompatibility, and can be well matched with human body bone modulus.In addition, the preparation method of the present application is simple to operate, and will not cause damage to the strength of fiber body, the preparation cost is low, environmental protection, suitable for industrial production, and the short carbon fiber composite material provided by the present application is also particularly suitable for 3D printing to form the final target product.

Description

Technical Field

[0001] This invention belongs to the field of polyetheretherketone composite material technology, and relates to a short carbon fiber reinforced polyetheretherketone composite material, its preparation method and application, specifically to a bioactive short carbon fiber reinforced polyetheretherketone composite material, its preparation method and application, and the short carbon fiber composite material provided by this invention is also suitable for 3D printing. Background Technology

[0002] In modern medicine, fracture repair has become a key focus of clinical treatment. With the increasing aging population and heightened social activity, the demand for orthopedic repair materials is experiencing explosive growth. However, while titanium alloy repair materials, widely used clinically, offer advantages such as high strength and corrosion resistance, their elastic modulus (approximately 120 GPa) is much higher than that of human bone tissue (approximately 20 GPa), easily leading to stress shielding effects and inhibiting bone regeneration. Furthermore, the X-ray blocking properties of titanium alloy repair materials also pose challenges to the observation and evaluation of postoperative bone healing.

[0003] Carbon fiber / poly(Ether-Ether-Ketone), CF / PEEK composites are promising orthopedic materials due to their mechanical properties, biocompatibility, and low density, which are similar to those of bone tissue. They also inherit the non-toxicity, good chemical resistance, natural radiation permeability, and even magnetic resonance imaging compatibility of PEEK. This has made them a research hotspot in recent years. However, there are still areas for improvement before CF / PEEK composites can be used as load-bearing orthopedic materials. Firstly, the smooth surface of CF prevents effective mechanical engagement with PEEK. Secondly, CF's chemical inertness and low surface energy prevent chemical bonding with PEEK. These factors contribute to poor compatibility and weak interfacial interaction between CF and PEEK. When external loads are applied to the fiber-reinforced resin composite, the interface cannot effectively transfer stress, leading to excessive stress and interfacial cracking, ultimately causing the entire composite material to fail. On the other hand, to effectively achieve bone regeneration and fracture healing, integration of implant materials with surrounding bone tissue is crucial. However, CF / PEEK lacks bioactivity, hindering cell growth and adhesion. Furthermore, its poor osteogenic integration ability prevents it from forming a strong bond with human bone tissue after implantation, thus affecting the long-term stability of the implant material within the body. These problems severely impede the clinical application of CF / PEEK composite materials.

[0004] In CF / PEEK composites, there are three main components: CF as the reinforcing phase, PEEK matrix as the continuous phase, and interfacial phase connecting CF and PEEK. The interfacial phase is an important bridge for the transfer of properties between the fiber and the matrix. In the study of interface modification of composites, improving the interfacial properties is crucial to improving the overall mechanical properties of composites. Good interfacial bonding can effectively transfer loads, thereby improving the mechanical properties of composites such as flexural strength and flexural modulus.

[0005] Currently, commonly used interface modification methods include carbon fiber modification and PEEK matrix modification. Modification methods for the PEEK matrix are generally more dangerous and complex. For example, the preparation process of sulfonated polyether ether ketone (PEEK) for PEEK matrix modification (reference 1) is complex and dangerous. Modification of the carbon fiber surface is a commonly used and efficient method. Surface modification of carbon fiber materials can improve the wettability of carbon fibers in the PEEK matrix to a certain extent, increase the bonding strength between the two, and thus improve the performance of the composite material.

[0006] Reference 2 describes the preparation of composite materials using sulfonated polyether ether ketone grafting, room-temperature concentrated nitric acid treatment, high-temperature water bath concentrated nitric acid treatment, mixed acid (nitric acid + concentrated sulfuric acid) ultrasonic treatment, and removal of only the surface oxide layer from polyacrylonitrile-based carbon fibers and PEEK. The results show that the carbon fiber wetting effect is better after 20 minutes of mixed acid ultrasonic treatment, which is more conducive to composite material preparation and has the best effect on enhancing the mechanical properties of the material.

[0007] Reference 3 discloses an interface modification method for carbon fiber reinforced polyetheretherketone (PEEK) composites. This method uses polyetherimide (PEI) and polyetherimide / graphene oxide (PEI / GO) to modify the interface of carbon fibers activated with 37 wt% concentrated nitric acid, followed by compression molding to prepare CF / PEEK composites. The results show that 1 wt% PEI effectively enhances the fiber-matrix interaction force, and the addition of 0.5 wt% GO further improves the interfacial bonding performance, increasing interlaminar shear strength by 68%, flexural strength by 54%, and flexural modulus by 68%.

[0008] Reference 4 discloses a method for preparing modified carbon fiber reinforced polyetheretherketone (PEEK) composites, comprising: 1) immersing carbon fiber bundles in an extract of an organic solvent to obtain degummed carbon fibers; immersing the degummed carbon fibers in a water / p-phenylenediamine mixture, adding isoamyl nitrite, stirring, filtering, and rinsing; 2) dispersing carbon nanoparticles in water by ultrasonication, immersing the carbon fibers in the carbon nanoparticle dispersion, adding isoamyl nitrite, stirring, filtering, and rinsing; 3) melting and granulating a mixture of PEEK and processing aids with the modified carbon fibers in a twin-screw extruder. This method uses a diazonium salt reaction to activate the carbon fibers and loads carbon nanoparticles onto the carbon fiber surface, improving the surface activity of the carbon fibers and enhancing the wettability between the fibers and the resin; the modified carbon fibers have good mechanical bonding with PEEK resin, effectively improving the mechanical properties of the composite material.

[0009] Reference 1: CN108047470A

[0010] Reference 2: Wei Jiashun, Pan Lei, Tao Jie, et al. Effects of surface treatment on the wettability of carbon fiber and tensile properties of continuous fiber reinforced PEEK composites [J]. Fiber Composites, 2010, 4: 36-40.

[0011] Reference 3: Sun Yijian, Wu Ju, Elwathig AM Hassan, et al. Interfacial modification of carbon fiber reinforced polyetheretherketone composites [J]. High Technology Fibers & Applications, 2021, 46(02): 21-27.

[0012] Reference 4: CN105219018A Summary of the Invention

[0013] The problem the invention aims to solve

[0014] As mentioned above, although existing technologies have been used to study the modification of carbon fiber surfaces, most modified carbon fiber reinforced polyether ether ketone composites are treated with acid solutions (e.g., references 2 and 3). However, acid solutions can damage the carbon fiber surface, and the damaged carbon fiber surface has a significant impact on the mechanical properties of the composite material.

[0015] The modification method cited in reference 4 effectively improves the surface activity of carbon fibers and greatly enhances the mechanical strength of carbon fiber composites without damaging the strength of the fiber itself. However, it does not bring any biological activity to the carbon fiber / polyether ether ketone composite, and therefore cannot achieve the goal of being used to prepare bone repair materials.

[0016] In summary, there is an urgent need to improve the inert surface of carbon fibers and develop a carbon fiber-reinforced polyetheretherketone (PEEK) composite material whose mechanical properties are compatible with the growth environment required by human bones. Furthermore, it should possess certain bioactivity to ensure its applicability in the human body without causing rejection. The key to solving the challenges of applying CF / PEEK composite materials to the preparation of bone repair materials lies in perfectly combining these two aspects.

[0017] Therefore, to address the shortcomings of existing technologies, the present invention aims to provide a carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material that simultaneously possesses good interfacial bonding, bioactivity, and biocompatibility, is non-toxic and harmless, and is easy to industrially produce, along with its preparation method and applications. The CF / PEEK composite material of the present invention overcomes the problem that existing CF / PEEK composite materials cannot simultaneously achieve good mechanical properties and bioactivity. Furthermore, its preparation method is simple to operate, conducive to large-scale production, and does not affect the intrinsic properties of the carbon fiber material. In particular, the method described above also solves the problem that CF / PEEK composite materials cannot be used to prepare bone repair materials due to their 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 product.

[0018] Solution for solving the problem

[0019] It has been found that the above-mentioned technical problems can be solved by implementing the following technical solutions:

[0020] [1]. The present invention provides a short carbon fiber reinforced polyether ether ketone composite material, wherein the composite material comprises a polyether ether ketone matrix as a continuous phase, short carbon fibers as a reinforcing phase, and the surface of the short carbon fibers has a modified layer;

[0021] The bioactive components in the modified layer include β-tricalcium phosphate and aluminum-containing phosphate.

[0022] [2]. According to the composite material described in [1], the content of the short carbon fiber as the reinforcing phase is 10 to 30 wt% based on the total mass of the composite material.

[0023] [3]. The composite material according to [1] or [2], wherein the short carbon fibers are either unoriented or oriented along any axial direction in the composite material.

[0024] [4]. The composite material according to [1] or [2], wherein the length of the short carbon fiber is 10~500 μm.

[0025] [5]. The composite material according to [1] or [2], wherein the aluminum phosphate includes one or two of calcium aluminum phosphate and aluminum phosphate; the modified layer is obtained by electrodeposition in an electrolyte containing a calcium source and a phosphorus source, wherein the molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:1; and the thickness of the modified layer is less than 1 μm.

[0026] [6]. The present invention also provides a method for preparing a short carbon fiber reinforced polyether ether ketone composite material according to any one of [1]-[5], wherein the preparation method comprises the following steps:

[0027] 1) Steps for surface modification of short carbon fibers: using an acidic solution containing calcium and phosphorus sources as the electrolyte and aluminum sheets as the anode and cathode, short carbon fibers are electrodeposited and then sintered in an oxygen-free environment to obtain short carbon fiber powder with a modified layer on the surface; before electrodeposition, the short carbon fibers have been subjected to plasma oxidation treatment.

[0028] 2) Mixing step: Use a solvent to mix the short carbon fiber powder with the modified layer on the surface and the polyether ether ketone powder evenly, filter, and dry to obtain the mixed powder;

[0029] 3) Compression molding step: The mixed powder is compression molded to obtain short carbon fiber reinforced polyether ether ketone composite material.

[0030] [7]. According to the preparation method described in [6], wherein in step 1),

[0031] The pH value of the electrolyte is 3-5;

[0032] The molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:1.

[0033] [8]. According to the preparation method described in [6] or [7], wherein, in step 1),

[0034] The conditions for plasma oxidation treatment include: power of 5~50W, time of 10s~5min, and gas source of any one of oxygen, argon, nitrogen, or air.

[0035] [9]. According to the preparation method described in [6] or [7], wherein, in step 2),

[0036] The solvent is an alcohol;

[0037] The mass ratio of the short carbon fiber powder with the modified layer on the surface to the polyetheretherketone powder is 1:(3~5).

[0038]

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

[0039] The effects of the invention

[0040] Based on the implementation of the above technical solution, the present invention can achieve the following technical effects:

[0041] In the short carbon fiber reinforced polyetheretherketone (PEEK) composite material prepared by this invention, intermolecular forces such as hydrogen bonds and van der Waals forces are generated between the carbon fibers and the PEEK matrix, resulting in a stronger bond with the PEEK matrix and making it less prone to detachment. Furthermore, hydrogen bonds are also generated between the carbon fibers and the bioactive components (β-tricalcium phosphate and aluminum phosphate) in the modified layer. This yields a uniform and ordered short carbon fiber reinforced PEEK composite material with excellent mechanical properties, bioactivity, and biocompatibility. It can well match the modulus of human bones, better meet the requirements of modern orthopedic medical applications, and is expected to be applied in the field of load-bearing orthopedics.

[0042] The preparation method of the present invention effectively improves the bioactivity of carbon fiber surface and greatly enhances the mechanical properties of carbon fiber reinforced polyether ether ketone composite material, without damaging the strength of the fiber itself. It has low preparation cost, is environmentally friendly, and is suitable for industrial production.

[0043] The short carbon fiber composite material of the present invention is also suitable for various 3D printing preparations of final products, thus having extremely high degree of freedom in use and molding. Attached Figure Description

[0044] Figure 1 This is a process flow diagram for preparing the short carbon fiber reinforced polyetheretherketone composite material of the present invention;

[0045] Figure 2 These are optical microscope images of the short carbon fibers before and after modification according to the present invention.

[0046] Figure 3 The images show SEM images of the short carbon fibers before and after modification according to this invention.

[0047] Figure 4 This is a magnified SEM image of the modified short carbon fiber ECF20 in Example 1 of the present invention;

[0048] Figure 5 This is an EDS elemental analysis diagram of the surface of the modified short carbon fiber ECF20 in Example 1 of the present invention;

[0049] Figure 6 The X-ray diffraction pattern of the inorganic non-metallic material coating in Embodiment 1 of the present invention;

[0050] Figure 7 This is a phase composition diagram of the inorganic non-metallic material coating in Example 1 of the present invention;

[0051] Figure 8 The figure shows the static contact angle test results of the short carbon fibers before and after the modification of the present invention.

[0052] Figure 9 The image shows the surface energy test results of the short carbon fibers before and after modification according to this invention.

[0053] Figure 10 The figures show the flexural strength test results of the short carbon fiber reinforced polyetheretherketone composite materials prepared in various embodiments and comparative examples of the present invention.

[0054] Figure 11 The graph shows the flexural modulus test results of the short carbon fiber reinforced polyetheretherketone composite materials prepared in various embodiments and comparative examples of the present invention.

[0055] Figure 12 Comparison of cross-sectional SEM morphology of short carbon fiber reinforced polyether ether ketone composite materials prepared in various embodiments and comparative examples of the present invention.

[0056] Figure 13 These are enlarged SEM images comparing the cross-sectional morphology of short carbon fiber reinforced polyether ether ketone composite materials prepared in various embodiments and comparative examples of the present invention. Detailed Implementation

[0057] The following describes embodiments of the present invention, but the invention is not limited thereto. The present invention is not limited to the configurations described below; various modifications can be made within the scope of the claims. Embodiments and examples obtained by appropriately combining the disclosed technical means in different embodiments and examples are also included within the technical scope of the present invention. Furthermore, all documents described in this specification are incorporated herein by reference.

[0058] Unless otherwise defined, the technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0059] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0060] Unless otherwise required in this application, throughout the specification and the claims, the word "comprising" shall be interpreted in an open-ended, inclusive sense, meaning "including but not limited to".

[0061] Unless otherwise stated, in this instruction manual, "more" in "multiple", "multi-variety", "multiple", etc., means a value of 2 or more.

[0062] In this specification, the terms "substantially" or "truly" mean that the error compared to the relevant perfect or theoretical standard is less than 1%, or less than 0.8%, or less than 0.6%. Furthermore, when "all" or "entire" is used in this specification, it also means "all" or "entire" in the sense of "substantially" or "truly".

[0063] Unless otherwise specified, "%" in this instruction manual refers to the percentage content by mass.

[0064] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0065] In this specification, "optional" or "optionally" means that the event or situation described below may or may not occur, and the description includes both the scenario in which the event occurs and the scenario in which the event does not occur.

[0066] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0067] In this instruction manual, when "room temperature" or "room temperature" is used, the temperature can be 23±2℃.

[0068] First aspect

[0069] A first aspect of the present invention provides a short carbon fiber reinforced polyether ether ketone composite material, particularly a bioactive short carbon fiber reinforced polyether ether ketone composite material, wherein the composite material comprises a polyether ether ketone matrix as a continuous phase, short carbon fibers as a reinforcing phase, and the surface of the short carbon fibers has a modified layer.

[0070] (Polyetheretherketone)

[0071] Polyetheretherketone (PEEK) is a member of the polyaryletherketone family. It consists of an aromatic molecular backbone and ketone and ether functional groups between aromatic rings. The strong benzene ring, flexible ether, and carbonyl groups that enhance intermolecular attraction form the molecular structure of PEEK. This chemical structure gives PEEK the following excellent properties: 1) Heat resistance: PEEK has a glass transition temperature of 143℃ and a melting temperature of 334℃. Carbon fiber reinforced PEEK composites can be used at 260℃, and its heat distortion temperature is as high as 300℃; 2) Abrasion resistance: PEEK's excellent abrasion resistance is comparable to that of polyimide; 3) Flame retardancy: It produces only a small amount of smoke and toxic gases when burning; 4) Hydrolysis resistance: PEEK can be used in hot water or steam environments at 300℃; 5) Chemical resistance: PEEK has high resistance to many chemicals; 6) Biocompatibility: PEEK's biocompatibility is close to that of titanium alloys, and it is widely used as an internal implant in spinal surgery, joint surgery, trauma surgery, and bone defect repair.

[0072] (Short carbon fiber)

[0073] Short carbon fiber is a fibrous 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.

[0074] In this invention, the size of the short carbon fibers is not particularly limited in principle; they can be self-made or commercially available. In some preferred embodiments, the particle size of the short carbon fibers is 10~500μm, preferably 10~120μm, and the fiber diameter is 0.1~10μm. Therefore, it can be understood that the carbon fibers have micrometer-level dimensions in the particle size (length or particle size) direction and nanometer to micrometer-level dimensions in the fiber (cross-sectional) diameter.

[0075] Furthermore, the description of the particle size of short carbon fibers is not limited to the length of tiny single fiber particles. It goes without saying that the particle size of the short carbon fibers described above in this invention should be understood as the maximum size of an independent fiber particle (which can be a single fiber or an aggregate 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 cluster, the particle size is the diameter of the fiber cluster.

[0076] In some specific implementations, the short carbon fibers in the composite material are either unoriented or oriented along any axial direction. Specifically, when the short carbon fibers in the composite material are unoriented, i.e., 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 molded, mechanical stretching can orient the fibers to a certain extent along the stretching direction. Oriented fibers can significantly improve the strength and stiffness of the material in a specific direction. Therefore, the orientation of the short carbon fibers needs to be designed and controlled according to specific application requirements.

[0077] In some specific embodiments, the content of the short carbon fibers as the reinforcing phase is 10-30 wt% based on the total mass of the composite material, preferably 15-25 wt%, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, etc.

[0078] In some specific embodiments, the thickness of the modified layer of the present invention is less than 1 μm, preferably less than 800 nm, more preferably less than 600 nm, even more preferably 100~600 nm, and more preferably 300~600 nm.

[0079] In some specific implementations, the modified layer is obtained by electrodeposition in an electrolyte containing a calcium source and a phosphorus source, wherein the molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:1.

[0080] In some specific implementations, the bioactive components in the modified layer include β-tricalcium phosphate and aluminum phosphate.

[0081] In some preferred embodiments, the aluminum-containing phosphate includes one or both of calcium aluminum phosphate and aluminum phosphate.

[0082] (β-tricalcium phosphate)

[0083] 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 crystalline form of calcium phosphate and possesses the following excellent properties: 1) Biocompatibility: Compatible with human tissues, suitable for biomedical applications; 2) Biodegradability: Gradually degrades in the body and can be replaced by new bone; 3) Osteoconductivity: Promotes new bone growth; 4) Mechanical Properties: Possesses a certain mechanical strength, suitable for load-bearing areas. This type of material is widely used in biomedical fields such as bone repair. After implantation, it fuses directly with bone without any local inflammatory reactions or systemic toxicity.

[0084] (Calcium aluminum phosphate)

[0085] Calcium aluminum phosphate is an important inorganic compound, generally referring to a complex phosphate material containing calcium (Ca), aluminum (Al), phosphorus (P), and oxygen (O). Its chemical composition can be represented as Ca... x Al y (PO4) z The specific structure of calcium aluminum phosphate may vary depending on the ratio of calcium, aluminum, and phosphorus, and it possesses the following excellent properties: 1) Biocompatibility: Calcium aluminum phosphate materials have good biocompatibility with human tissues and are commonly used in bone repair and dental materials; 2) Bioactivity: It can form chemical bonds with bone tissue, promoting 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. These materials have wide applications in biomedical fields such as bone repair, and are particularly studied due to their biocompatibility and bioactivity.

[0086] (Aluminum phosphate)

[0087] Aluminum phosphate (AlPO4) is an important inorganic compound composed of aluminum (Al), phosphorus (P), and oxygen (O). It exhibits good biocompatibility and has wide applications in biomedical fields such as bone repair. Studies have shown that the bioactivity of aluminum phosphate is limited, but its bioactivity can be significantly enhanced by combining it with bioactive materials such as β-TCP and calcium aluminum phosphate, thus giving it potential application value in bone repair.

[0088] The short carbon fiber reinforced polyether ether ketone composite material of the present invention has good bioactivity and biocompatibility. When used as a human tissue repair material, especially a bone repair material, it can effectively promote the healing or repair of human tissues without causing any adverse effects.

[0089] Second aspect

[0090] A 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:

[0091] 1) Steps for surface modification of short carbon fibers: using an acidic solution containing calcium and phosphorus sources as the electrolyte and aluminum sheets as the anode and cathode, short carbon fibers are electrodeposited and then sintered in an oxygen-free environment to obtain short carbon fiber powder with a modified layer on the surface; before electrodeposition, the short carbon fibers have been subjected to plasma oxidation treatment.

[0092] 2) Mixing step: Use a solvent to mix the short carbon fiber powder with the modified layer on the surface and the polyether ether ketone powder evenly, filter, and dry to obtain the mixed powder;

[0093] 3) Compression molding step: The mixed powder is compression molded to obtain short carbon fiber reinforced polyether ether ketone composite material.

[0094] In some specific embodiments of the present invention, a pretreatment step of the short carbon fibers may optionally be included before the step of surface modification of the short carbon fibers.

[0095] (Pretreatment of short carbon fiber powder)

[0096] The purpose of pretreatment of short carbon fiber powder is mainly to remove the slurry on the surface of the short carbon fiber powder, which is beneficial for subsequent surface oxidation treatment.

[0097] Specifically, the pretreatment steps of the short carbon fiber powder include: placing a certain amount of short carbon fiber powder in acetone and washing and removing the surface slurry while stirring.

[0098] In some specific embodiments of the present invention, the pretreatment conditions of the short carbon fiber powder include: a temperature of 10~40℃, preferably 15~30℃, a rotation speed of 100~800rpm, preferably 200~600rpm, and a time of 0.5~48h, preferably 1~24h.

[0099] Furthermore, the cleaned short carbon fiber powder is filtered and dried to remove residual acetone, and then it can be taken out for use.

[0100] In some specific embodiments of the present invention, there are no particular restrictions on the drying conditions. For example, the drying temperature can be 40~180℃, preferably 60~150℃; the drying time can be 0.5~48h, preferably 1~24h.

[0101] In addition, to improve the interfacial properties between carbon fibers and the matrix resin, industrial processes typically involve oxidizing the carbon fiber surface to impart active oxygen-containing functional groups such as hydroxyl and carbonyl groups. Common methods include anodic oxidation, nitric acid oxidation, and potassium permanganate oxidation. However, these methods can easily damage the carbon fiber surface and impair its mechanical properties. Therefore, to improve the interfacial properties between carbon fibers and the matrix resin (especially polyetheretherketone) without damaging the fiber surface, this invention employs plasma oxidation to oxidize the carbon fiber surface, enriching it with various active functional groups.

[0102] (Steps of plasma oxidation treatment)

[0103] In the plasma oxidation treatment step of the present invention, the surface of the short carbon fiber 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.

[0104] The polar groups that can be selected in the plasma oxidation process of this invention include one or more polar oxygen-containing functional groups such as carbonyl and hydroxyl.

[0105] In some specific embodiments of the present invention, the surface of short carbon fibers is subjected to plasma oxidation treatment at a power of 5~50W for 10s~5min until oxygen-containing functional groups are formed on the surface, thereby obtaining oxidized short carbon fibers.

[0106] 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, with oxygen being preferred.

[0107] It should be noted that the plasma oxidation treatment steps described above are merely to introduce more polar groups to facilitate the activity of the subsequent modified layer bonding. For example, in the above oxidation treatment, certain active groups can be imparted to the carbon fiber surface. Therefore, this treatment only increases the energy or energy level of the carbon fiber surface by introducing specific active groups, rather than forming a complete hydrophilic modified layer. Consequently, the plasma oxidation treatment steps described above in this invention are not sufficient to cause any loss in the properties (especially mechanical properties) of the carbon fiber material itself.

[0108] (Steps of electrodeposition)

[0109] In the electrodeposition step of the present invention, an acidic solution containing calcium and phosphorus sources is used as the electrolyte, and aluminum sheets are used as the anode and cathode to electrodeposit oxidized short carbon fibers to form an inorganic non-metallic material precursor coating on their surface.

[0110] In some specific implementations, the preparation of the electrolyte includes the following steps:

[0111] a) Raw material dissolution

[0112] Add the calcium and phosphorus sources to deionized water at a certain molar ratio, and stir thoroughly to ensure that the calcium and phosphorus sources are completely dissolved to form a homogeneous mixed solution.

[0113] b) Adjust pH

[0114] The pH of the mixed solution is adjusted to alkaline (e.g., 8-10, preferably 9) by adding an alkaline solution (e.g., ammonia or sodium hydroxide solution). Under alkaline conditions, calcium and phosphorus will form an insoluble precipitate (e.g., calcium phosphate precursor).

[0115] c) Separation by static setting

[0116] Let it stand for a period of time to allow the precipitate to settle, and then separate the supernatant and suspension.

[0117] d). Dialysis

[0118] To remove small molecule impurities and unreacted ions from the suspension, the suspension is placed in a dialysis bag and dialyzed in deionized water. Furthermore, to improve dialysis efficiency and ensure sufficient removal of impurity ions, the deionized water used for dialysis can be changed multiple times during the dialysis process.

[0119] e) Adjusting pH

[0120] After dialysis, the pH 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. This indicates that the calcium and phosphorus compounds have completely dissolved and formed a stable electrolyte.

[0121] In this invention, the types of calcium sources that can be used can be selected from water-soluble calcium salts or their hydrates, such as calcium nitrate, calcium halide (except F), calcium chlorate, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate, calcium formate, calcium acetate, or one or more of their hydrates.

[0122] In this invention, the phosphorus source that can be used can be selected from one or more of soluble phosphates, hydrogen phosphates, and dihydrogen phosphates, such as 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.

[0123] In this invention, the acidic solutions that can be used can be selected from solutions formed from one or more inorganic or organic acids. More specifically, these acidic solutions can be selected from aqueous solutions formed from one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, formic acid, acetic acid, propionic acid, etc. Nitric acid is more preferred.

[0124] In some specific embodiments of the present invention, the pH value of the electrolyte is 3 to 5, preferably 3.2 to 4.5, 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.

[0125] 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, 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.

[0126] This invention has found that during electrodeposition, when the current intensity is low, the applied electric field cannot provide sufficient driving force, resulting in fewer nucleation points on the carbon fiber surface near the cathode, and virtually no coating is formed. As the current intensity increases, the number of nuclei increases, the grain distribution on the fiber surface becomes uniform, and ions form a uniform inorganic non-metallic precursor coating on the carbon fiber surface. When the current intensity is between 10 and 30 mA, it can be observed that the grains grow in a direction perpendicular to the fiber surface, with uniform grain size and distribution. When the current intensity further increases, since new nucleation points cannot be formed on the fiber surface, the inorganic non-metallic material begins to grow from dense growth to multi-layered growth in a flower-like pattern, the coating thickness increases, and even coating cracking occurs. The hydrogen evolution effect caused by excessively high current intensity is also not conducive to obtaining a uniform and dense inorganic non-metallic precursor coating.

[0127] In some specific embodiments of the present invention, the electrodeposition conditions include: a current intensity of 10-30 mA, preferably 15-25 mA; an electrodeposition time of 0.2-1 h, preferably 0.3-0.7 h; and an electrodeposition temperature of 40-60 °C, preferably 45-55 °C. Controlling the electrodeposition conditions within these ranges facilitates the formation of a uniform inorganic non-metallic precursor coating on the carbon fiber surface.

[0128] (Steps of oxygen-free sintering)

[0129] In the oxygen-free sintering step of the present invention, the main objective is to transform the inorganic non-metallic material precursor coating formed on the surface of short carbon fibers into an inorganic non-metallic material coating through oxygen-free sintering treatment.

[0130] In some specific embodiments of the present invention, the oxygen-free sintering is carried out under the protection of an inert gas. The present invention does not particularly limit the inert gas; it can be any gas commonly used in the art that does not participate in chemical reactions, such as nitrogen or argon.

[0131] In some specific embodiments of the present invention, the conditions for oxygen-free sintering include: heating to 450~900℃ and sintering for 2~6 hours, wherein the heating rate is 1~10℃ / min, preferably 3~8℃ / min.

[0132] (The mixing steps)

[0133] In the mixing step of the present invention, the short carbon fiber powder with a modified layer (i.e., an inorganic non-metallic material coating) on ​​the surface and the polyether ether ketone powder are mixed evenly using a solvent, filtered, and dried to obtain a mixed powder.

[0134] In this invention, there are no particular restrictions on the specific type of solvent, as long as it does not damage the structure and composition of carbon fiber and polyetheretherketone.

[0135] In some preferred embodiments, from the viewpoint of facilitating the implementation of uniform mixing, 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.

[0136] In some particularly preferred embodiments, the solvent of the present invention is anhydrous ethanol.

[0137] In some preferred embodiments, the mass ratio of the short carbon fiber powder with the 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.

[0138] In the mixing step, in some preferred embodiments, from the viewpoint of better achieving the effects of the invention, the solvent content is preferably 50-99% by mass, more preferably 60-95% by mass, and even more preferably 80-90% by mass, relative to the total mass of the mixing system.

[0139] In some specific embodiments, the mixing is preferably carried out under dynamic action. In this invention, there are no particular limitations on the method used to apply the dynamic action; it can be a method known in the art, such as mechanical stirring, ultrasonic irradiation, or magnetic stirring using a high-speed mixer, high-speed shear emulsifier, ball mill, hammer mill, vortex mixer, or vibrator. In some preferred embodiments, magnetic stirring can be used.

[0140] In addition, the present invention does not have any particular limitation on the mixing temperature; preferably, it can be carried out at 10~40°C.

[0141] The drying process can be carried out using various methods known in the art, such as air drying, natural air drying, oven hot air drying, etc.

[0142] The present invention does not impose any particular restrictions on drying conditions. For example, the drying temperature can be 40~180℃, preferably 60~150℃; the drying time can be 0.5~48h, preferably 1~24h.

[0143] (Steps of compression molding)

[0144] In the compression molding step of the present invention, the mixed powder is compression molded to obtain a short carbon fiber reinforced polyether ether ketone composite material.

[0145] In some specific implementations, the molding conditions include: a first stage: heating from room temperature to 300~400℃, holding at that temperature for 0.1~1h, and holding at a pressure of 2~5MPa; a second stage: cooling to 100~160℃, and holding at a pressure of 2~5MPa; and a third stage: depressurizing and air cooling to room temperature; wherein the heating rate is 1~10℃ / min, preferably 4~8℃ / min, and the cooling rate is 1~10℃ / min, preferably 3~8℃ / min.

[0146] Third aspect

[0147] A third aspect of the present invention provides the use 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 repair materials of desired shapes by 3D printing.

[0148] Furthermore, the short carbon fiber reinforced polyetheretherketone composite material constructed according to the present invention has a flexural strength of 50-300 MPa, preferably 100-150 MPa, and a flexural modulus of 2-30 GPa, preferably 4-8 GPa. These properties are well-matched with the modulus of human bones and hold promise for application in the field of load-bearing orthopedics.

[0149] Example

[0150] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0151] Example 1:

[0152] A method for preparing short carbon fiber reinforced polyetheretherketone composite material, such as... Figure 1 As shown, it includes the following steps:

[0153] S1. Cleaning: Add a certain amount of short carbon fiber powder to acetone, stir at 400 rpm for 10 hours at room temperature, filter, and dry at 120℃ for 12 hours to obtain clean short carbon fiber powder for later use.

[0154] S2. Plasma oxidation treatment: The cleaned short carbon fiber powder is placed in a plasma cleaner for plasma oxidation treatment (gas source is oxygen, power is 29.6W, treatment time is 2min) to obtain oxidized short carbon fiber powder.

[0155] Electrolyte preparation:

[0156] 0.656 g of calcium nitrate tetrahydrate and 0.352 g of diammonium hydrogen phosphate were added to 200 mL of deionized water and stirred (the molar ratio of calcium to phosphorus was 1:1). The pH of the solution was adjusted to 9 with ammonia until a large amount of white precipitate formed. The supernatant and suspension were separated by standing. The suspension was placed in a dialysis bag and dialyzed in deionized water for 21 hours, with the deionized water being replaced at 3, 6, and 10 hours. After dialysis, the pH of the suspension was adjusted to 3.8 with concentrated nitric acid until a clear solution was formed, which is the electrolyte for electrodeposition.

[0157] S3. Electrodeposition: Using aluminum sheets as anode and cathode (the cathode aluminum sheet is placed at the bottom of a beaker containing electrolyte, and the anode aluminum sheet is placed in the upper part of the beaker containing electrolyte), oxidized short carbon fiber powder is added to the electrolyte. The oxidized short carbon fiber powder will spontaneously settle onto the bottom cathode aluminum sheet. Under the conditions of 50℃ temperature and 20mA current, it is energized for 30min, filtered, and dried at 80℃ for 12h to obtain short carbon fiber powder with an inorganic non-metallic material precursor coating on the surface.

[0158] The chemical reaction formula for the electrodeposition process is as follows:

[0159]

[0160]

[0161] .

[0162] S4. Oxygen-free sintering: Under argon protection, short carbon fiber powder with an inorganic non-metallic precursor coating on its surface is placed in a tube furnace for oxygen-free sintering treatment (heating from 50°C to 450°C at a rate of 5°C / min and holding at that temperature for 1 hour, then heating from 450°C to 900°C at a rate of 5°C / min and holding at that temperature for 3 hours, and then cooling from 900°C to 50°C at a rate of 5°C / min), to obtain short carbon fiber powder with an inorganic non-metallic coating on its surface, denoted as: ECF20.

[0163] The chemical reaction formula for the oxygen-free sintering process is as follows: .

[0164] S5. Powder mixing: Mix 5g of short carbon fiber powder with an inorganic non-metallic coating on the surface with 20g of PEEK powder in 300mL of anhydrous ethanol until homogeneous, filter, and dry at 120℃ for 12h to obtain a homogeneous mixed powder.

[0165] S6. Compression molding: Fill the mold with the mixed powder. First, use a hydraulic press to apply a pressure of 100MPa to compact the powder. Then, use a pneumatic press to apply and maintain a pressure of about 3.75MPa. Heat from 25℃ to 350℃ at a rate of 6℃ / min and hold at this temperature for 20min. Cool from 350℃ to 140℃ at a rate of 5℃ / min. Release the pressure and air cool to 25℃. Demold. Use a grinding and polishing machine to grind the upper and lower surfaces at a speed of 30rpm for 5~15min each to obtain short carbon fiber reinforced polyether ether ketone composite material, denoted as: ECF20 / PEEK.

[0166] Example 2:

[0167] The difference compared to Example 1 is that the current intensity used for electrodeposition is 30mA.

[0168] The short carbon fiber powder with an inorganic non-metallic material coating on its surface prepared in this embodiment is denoted as ECF30.

[0169] The short carbon fiber reinforced polyether ether ketone composite material prepared in this embodiment is denoted as ECF30 / PEEK.

[0170] Comparative Example 1:

[0171] A method for preparing a short carbon fiber reinforced polyetheretherketone composite material includes the following steps:

[0172] S1. Cleaning: Add a certain amount of short carbon fiber powder to acetone, stir at 400 rpm for 10 hours at room temperature, filter, and dry at 120℃ for 12 hours to obtain clean short carbon fiber powder, denoted as BCF.

[0173] S2. Powder mixing: Mix 5g of the cleaned short carbon fiber powder and 20g of PEEK powder evenly in 300mL of anhydrous ethanol, filter, and dry at 120℃ for 12h to obtain a uniform mixed powder.

[0174] S3. Compression molding: Place the mixed powder in a mold, first use a hydraulic press to apply a pressure of 100MPa to compact the powder, then use a pneumatic press to apply and maintain a pressure of about 3.75MPa, heat from 25℃ to 350℃ at a rate of 6℃ / min, and hold at this temperature for 20min, then cool from 350℃ to 140℃ at a rate of 5℃ / min, release the pressure, air cool to 25℃, demold, and use a grinding and polishing machine to grind the upper and lower surfaces at a speed of 30rpm for 5~15min each to obtain short carbon fiber reinforced polyether ether ketone composite material, denoted as: BCF / PEEK.

[0175] Test example:

[0176] 1. The changes in surface morphology of the short carbon fibers before and after modification were observed using optical microscopy and scanning electron microscopy (SEM). The optical micrographs are shown below. Figure 2 Its SEM image (magnification of 9000×) can be found here. Figure 3 .

[0177] Depend on Figure 2 and Figure 3 It can be seen that the surface of unmodified short carbon fiber (BCF) is smooth, while the surface of modified short carbon fiber (ECF20, ECF30) is not a smooth plane, but a rough structure composed of different particles.

[0178] Depend on Figure 3 It can be seen that the thickness of the coating on the surface of the short carbon fiber after surface modification is 300~600nm.

[0179] 2. The SEM image (magnification 37400×) of the surface of the short carbon fiber powder ECF20 with an inorganic non-metallic material coating obtained in Example 1 of this invention is shown below. Figure 4 Its energy dispersive spectroscopy (EDS) elemental analysis diagram is shown below. Figure 5 The X-ray diffraction pattern of its coating is shown in [reference needed]. Figure 6 The phase composition of its coating is shown in Figure 7 .

[0180] Depend on Figure 4It can be seen that the surface coating of the short carbon fiber ECF20 after surface modification treatment exhibits a flower-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 MA, SMIRNOV VV, PROTSENKO PV et al. Influence of aluminum substitutions on phase composition and morphology of β-tricalcium phosphate nanopowders [J]. Ceramics international, 2017, 43(16): 13881-13884.).

[0181] Depend on Figure 5 It can be seen that the main elements contained on the surface of the short carbon fiber after surface modification are C, O, Ca, P and Al. Since the surface of the short carbon fiber before modification only contains C and O, it can be seen that Ca, P and Al elements were successfully introduced into the surface of the short carbon fiber after surface modification.

[0182] Depend on Figure 6 It can be seen that the positions of the main diffraction peaks of the coating material are consistent with those of the standard card of Ca9Al(PO4)7 (PDF#48-1192), the standard card of β-TCP (PDF#09-0169), and the standard card of AlPO4 (PDF#72-1161), respectively, indicating that an inorganic non-metallic material coating was successfully prepared on the surface of short carbon fibers.

[0183] Depend on Figure 7 It is known that the inorganic non-metallic material coating is composed of 71.9wt% calcium aluminum phosphate (chemical formula Ca9Al(PO4)7), 5.3wt% β-tricalcium phosphate (abbreviated as β-TCP, chemical formula Ca3(PO4)2) and 22.8wt% aluminum phosphate (chemical formula AlPO4). All three substances have excellent biocompatibility and bioactivity.

[0184] 3. The wettability of the short carbon fibers before and after modification was characterized using a contact angle meter. The standard liquid for the static contact angle test was deionized water (γ=72.8mN / m, γ...). d =21.8 mN / m, γ p =51.0 mN / m) and the nonpolar solvent diiodomethane (γ=50.8 mN / m, γ d =50.8mN / m, γ p =0mN / m), the static contact angle test results of the short carbon fibers before and after modification are shown in Table 1 and Figure 8The polar and nonpolar components of the fiber were calculated based on the static contact angle between the short carbon fiber sample and the two liquids, and the surface energy of the short carbon fiber was finally calculated. The test results are shown in Table 1 and 2. Figure 9 .

[0185] Table 1:

[0186]

[0187] Depend on Figure 8 and Figure 9 It can be seen that the short carbon fiber without modification has the largest contact angle, indicating that the surface polarity and surface energy of the short carbon fiber material itself are very low. The contact angles of ECF20 and ECF30 are reduced to varying degrees, while the surface energy of ECF20 and ECF30 is increased to varying degrees. This shows that the introduction of inorganic non-metallic materials with good biocompatibility can improve the hydrophilicity and interfacial forces of short carbon fibers.

[0188] 4. Three-point bending tests were conducted on the short carbon fiber reinforced polyetheretherketone composites prepared in Comparative Example 1, Example 1, and Example 2 according to ASTM D790 standard. 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, ECF20 / PEEK exhibits improved flexural strength and flexural modulus, increasing by 11.65% and 1.04%, respectively. Studies have shown that the flexural strength of cortical bone is approximately 50–300 MPa, and the flexural modulus is approximately 5–30 GPa. The short carbon fiber reinforced polyetheretherketone composite material prepared in this invention has flexural strength and flexural modulus within these ranges, and is expected to be applied in the field of load-bearing orthopedics.

[0189] Table 2:

[0190]

[0191] 5. The cross-sectional morphology of the short carbon fiber reinforced polyetheretherketone composites prepared in Comparative Example 1, Example 1, and Example 2 was observed using SEM. The comparison images are shown below. Figure 12 (Magnification is 50×) and Figure 13 (Magnification is 600×).

[0192] Depend on Figure 12 It is known that the composite material has a porous structure with a pore size of approximately 200–400 μm. Researchers have found that porous PEEK with a pore size of 280–400 μm can improve osseointegration while maintaining the structural integrity required for load-bearing orthopedic applications, compared to non-porous PEEK. The short carbon fiber reinforced polyetheretherketone composite material prepared in this invention has a pore size close to this range and is expected to be applied in the field of load-bearing orthopedics.

[0193] Depend on Figure 13 It is evident that the cross-section of the unmodified short carbon fiber reinforced polyetheretherketone (PEEK) composite exhibits significant fiber pull-out from the PEEK matrix, and the carbon fiber surface is smooth with no PEEK adhering to it, resulting in lower mechanical properties of the composite. In contrast, the cross-section of the surface-modified short carbon fiber reinforced PEEK composite ECF20 / PEEK shows no fiber pull-out phenomenon, indicating that surface modification enhances fiber surface activity, facilitating wetting between the fiber and the PEEK matrix. This induces the formation of transcrystalline layers on the PEEK surface. When the composite is subjected to axial stress, the transcrystalline layer effectively transmits interfacial forces, improving its interfacial bonding strength.

[0194] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0195] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A short carbon fiber reinforced polyether ether ketone composite material, characterized by, The composite material comprises a polyether ether ketone matrix as a continuous phase, short carbon fibers as a reinforcing phase, and the surface of the short carbon fibers has a modified layer; The bioactive components in the modified layer comprise β-tricalcium phosphate and an aluminum-containing phosphate; the modified layer is obtained by electrodeposition via an electrolyte containing a calcium source and a phosphorus source, and the electrodeposition uses an aluminum sheet as an anode and a cathode.

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

3. The composite material according to claim 1 or 2, characterized in that, The short carbon fibers are non-oriented in the composite material or are oriented along any one axial 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 comprises one or both of calcium aluminum phosphate and aluminum phosphate; the molar ratio of calcium to phosphorus in the electrolyte is greater than 1:1 and less than 1.5:1; and the thickness of the modified layer is 1 μm or less.

6. A process for the production of a short carbon fiber reinforced polyether ether ketone composite according to any one of claims 1 to 5, characterized in that The preparation method comprises the following steps: 1) a step of surface modification of short carbon fibers: electrodeposition of short carbon fibers is performed using an acidic solution containing a calcium source and a phosphorus source as an electrolyte and using an aluminum sheet as an anode and a cathode, and then oxygen-free sintering is performed to obtain short carbon fiber powder having a modified layer on the surface; before the electrodeposition, the short carbon fibers have been subjected to plasma oxidation treatment; 2) a mixing step: the short carbon fiber powder having a modified layer on the surface and polyether ether ketone powder are mixed uniformly using a solvent, filtered, and dried to obtain mixed powder; 3) a step of compression molding: the mixed powder is compression molded to obtain a short carbon fiber reinforced polyether ether ketone composite material.

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

9. The production method according to claim 6 or 7, characterized by, In step 2), the solvent is an alcohol; the mass ratio of the short carbon fiber powder having a modified layer on the surface to the polyether ether ketone powder is 1:(3-5).

10. Use of the short carbon fiber reinforced polyether ether ketone composite material according to any one of claims 1-5 or the short carbon fiber reinforced polyether ether ketone 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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