Multifunctional artificial joint material with antibacterial / biological activity and preparation method thereof

Abstract

The present invention discloses a multifunctional artificial joint material with antibacterial / bioactivity and a preparation method thereof. The material comprises an antibacterial / bioactive layer composed of a copper sulfide / sulfonated polyetheretherketone composite material as a bottom layer, a mechanical performance enhancement layer composed of a graphene oxide / sulfonated polyetheretherketone composite material as an intermediate layer, and a wear-resistant layer composed of a carbon fiber / sulfonated polyetheretherketone composite material as a surface layer. In the method, a composite powder of copper sulfide and sulfonated polyetheretherketone, a composite powder of graphene oxide and sulfonated polyetheretherketone, and a composite powder of carbon fiber and sulfonated polyetheretherketone are prepared, and the three are hot-pressed to obtain a joint material. The artificial joint material of the present invention has good antibacterial properties and bioactivity that can effectively improve the artificial joint implant material, thereby greatly reducing the risk of postoperative infection of the artificial joint implant and enhancing the ability of bone ingrowth. The simultaneous optimization of the biotribology, biomechanics, antibacterial properties and bioactivity of the artificial joint material is achieved.

Description

Technical Field

[0001] The present invention relates to the field of artificial joint materials, in particular to a multifunctional artificial joint material with antibacterial / biological activity and a preparation method thereof. Background Art

[0002] Carbon fiber-reinforced polyetheretherketone (CF / PEEK) composites possess excellent biocompatibility and mechanical properties similar to natural bone. As an orthopedic implant material, CF / PEEK has been widely used in medical fields such as intervertebral disc fusion, orthopedics, and bone plates. CF / PEEK also exhibits excellent biotribological properties, making it an excellent artificial joint implant material, comparable to traditional ultra-high molecular weight polyethylene artificial joints. While traditional CF / PEEK artificial joint materials possess excellent biomechanical, biotribological, and biocompatibility properties, their lack of bioactivity and antibacterial properties is a bottleneck limiting their use as artificial joint implants.

[0003] It is well known that effectively improving the antibacterial properties of artificial joint implant materials and achieving long-term stability of joint prostheses are crucial for reducing the risk of postoperative infection and extending the lifespan of joint implants. On the one hand, the antibacterial properties of artificial joint prostheses are primarily achieved by adding various organic / inorganic nanoparticles with antibacterial properties to traditional artificial joint materials, thereby exerting an antimicrobial effect. However, the addition of inorganic nanoparticles can deteriorate other biological properties of artificial joint prostheses, such as biotribological and biomechanical properties. Therefore, optimizing both the antibacterial properties and biological performance of artificial joint prostheses remains a pressing issue. On the other hand, the long-term stability of artificial joint prostheses primarily relies on mechanical locking achieved through bone ingrowth at the bone-prosthesis interface. However, because the extent and degree of bone ingrowth on the prosthesis surface primarily depends on the bioactivity of the prosthetic material surface, long-term follow-up of currently used biofixed prostheses has revealed a high rate of aseptic loosening, limiting their application. Therefore, improving bone ingrowth on the prosthesis surface, increasing the strength and extent of adhesion between the prosthesis and the surrounding bone bed, and thus achieving long-term stability, remain key challenges that urgently need to be addressed in biofixed artificial joint prostheses. Summary of the Invention

[0004] The present invention provides a multifunctional artificial joint material with antibacterial / biological activity and a preparation method thereof, so as to solve the problems of poor antibacterial performance and weak biological fixation performance of artificial joint implant materials in the prior art.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A multifunctional artificial joint material with antibacterial / bioactive properties includes an antibacterial / bioactive layer, a mechanical performance enhancing layer, and a wear-resistant layer. The antibacterial / bioactive layer, the mechanical performance enhancing layer, and the wear-resistant layer are stacked to form a three-layer stacked structure, wherein the mechanical performance enhancing layer serves as the middle layer of the three-layer stacked structure. The material of the antibacterial / bioactive layer is a copper sulfide / sulfonated polyetheretherketone composite material, the material of the mechanical performance enhancing layer is a graphene oxide / sulfonated polyetheretherketone composite material, and the material of the wear-resistant layer is a modified carbon fiber / polyetheretherketone composite material.

[0007] Furthermore, in the copper sulfide / sulfonated polyetheretherketone composite material used as the antibacterial / bioactive layer material, the mass ratio of copper sulfide to sulfonated polyetheretherketone is 1:50~1:10.

[0008] Furthermore, in the graphene oxide / sulfonated polyetheretherketone composite material used as the mechanical property enhancement layer material, the mass ratio of graphene oxide to sulfonated polyetheretherketone is 1:100~1:10.

[0009] Furthermore, in the modified carbon fiber / polyetheretherketone composite material used as the wear-resistant layer material, the mass ratio of carbon fiber to polyetheretherketone is 1:10 to 1:2.

[0010] A method for preparing the above-mentioned multifunctional joint material with antibacterial / bioactivity comprises the following steps:

[0011] Step 1, preparing sulfonated polyetheretherketone powder using concentrated sulfuric acid solution and polyetheretherketone as raw materials;

[0012] Step 2: Using a soluble copper salt, a soluble sulfur source solution, and the sulfonated polyetheretherketone powder prepared in step 1 as raw materials, a composite powder of copper sulfide and sulfonated polyetheretherketone is prepared;

[0013] Composite powder of graphene oxide and sulfonated polyetheretherketone was prepared using graphene oxide, concentrated sulfuric acid solution and polyetheretherketone powder as raw materials.

[0014] A composite powder of modified carbon fiber and polyetheretherketone is prepared using carbon fiber, a mixed solution of concentrated nitric acid / concentrated sulfuric acid, and polyetheretherketone powder as raw materials;

[0015] Step 3. Hot-press the composite powder of copper sulfide and sulfonated polyetheretherketone, the composite powder of graphene oxide and sulfonated polyetheretherketone, and the composite powder of modified carbon fiber and polyetheretherketone obtained in step 2 and then cool them to room temperature to obtain an antibacterial / bioactive multifunctional joint material; wherein the hot pressing temperature during hot pressing is 320~380°C, the pressure is 10~15MPa, and the holding time is 20~30 min.

[0016] The further step 1 process is as follows:

[0017] Take concentrated sulfuric acid with a concentration of 95-98wt%, and add polyetheretherketone powder to the concentrated sulfuric acid solution while stirring the concentrated sulfuric acid solution at room temperature, wherein the mass ratio of polyetheretherketone to concentrated sulfuric acid solution is 1:2-1:3; after all the polyetheretherketone is added, continue stirring for 5-20 minutes, and then filter and wash to obtain sulfonated polyetheretherketone powder.

[0018] The preparation process of the composite powder of copper sulfide and sulfonated polyetheretherketone in step 2 is as follows:

[0019] First, the sulfonated polyetheretherketone prepared in step 1 is prepared into a suspension, and then a soluble copper salt is added to the suspension to obtain a sulfonated polyetheretherketone suspension containing copper ions;

[0020] Next, a soluble sulfur source solution is prepared;

[0021] Finally, the soluble sulfur source solution is added dropwise to the sulfonated polyetheretherketone suspension containing copper ions at a temperature of 60-80°C, and then stirred and reacted at a temperature of 60-80°C for 60-120 minutes. After the reaction is completed, the composite powder of copper sulfide and sulfonated polyetheretherketone is obtained after filtering and washing.

[0022] The molar ratio of copper ions in the soluble copper salt and sulfur ions in the soluble sulfur source solution is 1:1-1:1.5, and the mass ratio of the generated CuS to sulfonated polyetheretherketone is 1:50-1:10.

[0023] The preparation process of the composite powder of graphene oxide and sulfonated polyetheretherketone in step 2 is as follows:

[0024] Taking concentrated sulfuric acid with a concentration of 95-98 wt%, adding graphene oxide and polyetheretherketone to the concentrated sulfuric acid solution while stirring the concentrated sulfuric acid solution at room temperature, continuing to stir for 5-20 minutes after all the graphene oxide and polyetheretherketone powders are added, and then filtering and washing to obtain a composite powder of graphene oxide and sulfonated polyetheretherketone;

[0025] The mass ratio of the graphene oxide and polyetheretherketone mixed powder to concentrated sulfuric acid is 1:2~1:3.

[0026] The further step 2 is to prepare the composite powder of modified carbon fiber and polyetheretherketone as follows:

[0027] The polyetheretherketone powder and the carbon fiber are stirred and mixed to obtain a composite powder of the carbon fiber and the polyetheretherketone.

[0028] Furthermore, the carbon fiber is a carbon fiber modified by a mixed solution formed by concentrated nitric acid with a concentration of 65~68wt% and concentrated sulfuric acid with a concentration of 95~98wt%, wherein the volume ratio of concentrated nitric acid and concentrated sulfuric acid is 3:1, and the mass dosage ratio of the mixed solution and the carbon fiber is 1:2~1:3.

[0029] The design concept of the present invention: In order to effectively solve the antibacterial and bioactivity of existing carbon fiber (CF) / polyetheretherketone (PEEK) artificial joint materials and achieve effective improvement of comprehensive performance, the present invention uses the principles of bionics to construct a gradient bionic artificial joint material, and optimizes the overall performance of the artificial joint material by regulating the performance of each layer.

[0030] Specifically, the artificial joint fabricated in this invention has a three-layered structure. Considering the bottom layer of the artificial joint material, which comes into contact with natural tissue, it primarily provides antibacterial properties and bioactivity. Therefore, the bottom layer is composed of copper sulfide (CuS) nanoparticles with excellent antibacterial properties and a sulfonated polyetheretherketone (SPEEK) composite material (CuS / SPEEK), which also exhibits excellent bioactivity. The excellent antibacterial properties of the CuS nanoparticles effectively reduce the risk of postoperative infection. The excellent bioactivity of SPEEK, coupled with its ability to induce bone ingrowth, ensures long-term stability of the artificial joint prosthesis. The middle layer, composed of a sulfonated polyetheretherketone (SPEEK) composite material reinforced with graphene oxide (GO) (GO / SPEEK), boasts excellent mechanical properties and provides mechanical reinforcement and stress buffering, while also acting as a stress transmitter. The top layer, composed primarily of a carbon fiber (CF) and polyetheretherketone (PEEK) composite material (CF / PEEK), boasts excellent biotribological properties and biomechanical properties similar to those of natural bone, primarily providing friction reduction and anti-wear properties.

[0031] This invention uses the concept of bionics and a gradient design concept, adopts in-situ compounding and layer-by-layer laying combined with hot pressing technology to prepare a multifunctional joint material with antibacterial / bioactivity, so that the prepared joint material has wear resistance and excellent mechanical properties while giving it antibacterial and bioactive functions.

[0032] Compared with traditional artificial joint materials, the artificial joint material prepared by the present invention has the following advantages:

[0033] 1. The present invention adopts the concept of gradient design to achieve structural-functional integration of the artificial joint material. While having mechanical properties similar to those of natural joints, it also gives the artificial joint material more biological (antibacterial / bioactive) functions.

[0034] 2. The surface layer (friction layer) of the artificial joint prepared by this invention is composed of a CF / PEEK composite material with excellent tribological properties, which imparts excellent wear resistance. Furthermore, the carbon fibers, after modification and activation with mixed acid, enhance the interfacial bonding strength between the carbon fibers and the PEEK matrix, thereby effectively improving the mechanical properties of the CF / PEEK composite. Furthermore, because the CF / PEEK composite material has mechanical properties similar to those of natural joints, it can effectively mitigate the stress shielding effect between the artificial joint and natural bone caused by modulus mismatch. In particular, its polymeric flexibility significantly improves its ability to withstand physiological shock loads compared to traditional ceramic joint materials.

[0035] 3. In the present invention, the middle layer of the artificial joint material is composed of a GO / SPEEK composite material. On the one hand, GO, with its excellent mechanical strength, serves as a reinforcing phase in the GO / SPEEK composite material, thereby improving the mechanical properties of the artificial joint material. On the other hand, as a transition layer in the gradient artificial joint material, it also acts as a stress buffer layer, effectively transmitting stress in the gradient composite material. Furthermore, when GO is composited with SPEEK, the SPEEK surface, obtained by treating PEEK powder with concentrated sulfuric acid, contains abundant active groups. These groups can form good chemical bonds with active groups such as hydroxyl and carboxyl groups on the GO surface, thereby effectively improving the interfacial bonding performance of the GO / SPEEK composite material in the middle transition layer, ultimately leading to effective improvements in the mechanical properties of the GO / SPEEK composite material.

[0036] 4. In the present invention, the base layer of the artificial joint material (the layer in contact with natural tissue) is made of a CuS / SPEEK composite material. This has the advantage of effectively utilizing not only the highly effective antibacterial properties of CuS, but also the high bioactivity of SPEEK, achieving both antibacterial and bone growth-promoting effects. This improved antibacterial performance can effectively reduce the risk of postoperative infection after artificial joint implantation. At the same time, SPEEK's high bioactivity promotes bone growth, thereby accelerating the integration of the implanted joint material with natural bone tissue. Based on this, the present invention, based on the concept of gradient design, can achieve simultaneous optimization of the tribological, mechanical, and biological properties of new gradient artificial joint materials through the synergistic effects of the surface, intermediate, and base layer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of the composition of the antibacterial / bioactive multifunctional joint material of the present invention.

[0038] Figure 2 This is a diagram showing the antibacterial effect of the multifunctional artificial joint of the present invention (inhibition zone method).

[0039] Figure 3This is a diagram showing the antibacterial effect of the multifunctional artificial joint of the present invention (colony counting method).

[0040] Figure 4 Figure 3 shows the hydroxyapatite (bioactive) grown on the surface of the joint material before and after immersion in simulated body fluid, where: (a) is the surface morphology before immersion, and (b) is the surface morphology after immersion in simulated body fluid for 9 days. DETAILED DESCRIPTION

[0041] The present invention will be further described below with reference to the accompanying drawings and examples. Example 1

[0042] like Figure 1 As shown, this embodiment discloses a multifunctional artificial joint material with antibacterial / bioactive properties, including an antibacterial / bioactive layer, a mechanical performance enhancing layer, and a wear-resistant layer. These three layers are stacked to form a three-layer stacked structure, in which the antibacterial / bioactive layer is the bottom layer, the mechanical performance enhancing layer is the middle layer, and the wear-resistant layer is the surface layer.

[0043] In the three-layer stacked structure, the material of the antibacterial / bioactive layer as the bottom layer is a copper sulfide / sulfonated polyetheretherketone composite material, and the mass ratio of copper sulfide to sulfonated polyetheretherketone in the copper sulfide / sulfonated polyetheretherketone composite material is 1:50~1:10.

[0044] In the three-layer stacked structure, the material of the mechanical performance enhancement layer serving as the middle layer is a graphene oxide / sulfonated polyetheretherketone composite material, and the mass ratio of graphene oxide to sulfonated polyetheretherketone in the graphene oxide / sulfonated polyetheretherketone composite material is 1:100~1:10.

[0045] In the three-layer laminated structure, the material of the surface wear-resistant layer is a carbon fiber / polyetheretherketone composite material, and the mass ratio of carbon fiber to polyetheretherketone in the carbon fiber / polyetheretherketone composite material is 1:10~1:2. Example 2

[0046] This embodiment discloses a method for preparing the multifunctional joint material with antibacterial / bioactivity described in Example 1, comprising the following steps:

[0047] Step 1: Prepare sulfonated polyetheretherketone powder using concentrated sulfuric acid solution and polyetheretherketone as raw materials, and the process is as follows:

[0048] Take a concentrated sulfuric acid solution with a concentration of 98wt%, and add 100g of polyetheretherketone (PEEK) powder to the concentrated sulfuric acid solution while stirring the concentrated sulfuric acid solution at room temperature so that the concentrated sulfuric acid submerges the polyetheretherketone powder. After all the polyetheretherketone powder is added, continue stirring at room temperature for 8 minutes, then filter and repeatedly wash with distilled water to remove the concentrated sulfuric acid to obtain sulfonated polyetheretherketone (SPEEK) powder. Then, use a vacuum drying oven to dry the SPEEK powder at 60°C and set aside.

[0049] Step 2: Prepare composite powders of copper sulfide and sulfonated polyetheretherketone, composite powders of graphene oxide and sulfonated polyetheretherketone, and composite powders of carbon fiber and polyetheretherketone.

[0050] The preparation process of the composite powder of copper sulfide and sulfonated polyetheretherketone is as follows:

[0051] S1. 40 g of the SPEEK powder prepared in step 1 was added to 100 ml of deionized water and mechanically stirred for 30 min to prepare a SPEEK suspension. Subsequently, 2.11 g of copper chloride as a soluble copper salt was added to the SPEEK suspension under mechanical stirring to prepare a SPEEK suspension containing copper ions.

[0052] S2. Add 1.22 g of sodium sulfide as a soluble sulfur source to 60 ml of distilled water and stir magnetically at room temperature to fully dissolve it to prepare a sodium sulfide solution for use;

[0053] S3. Slowly add the sodium sulfide solution prepared in step S2 to the SPEEK suspension containing copper ions prepared in step S1, and maintain mechanical stirring at the same time, so that the sodium sulfide solution reacts with the copper ions to generate CuS particles in situ in the SPEEK suspension; after the addition is completed, continue the reaction for 90 minutes while stirring to fully react. The reaction temperature is maintained at 70°C throughout the entire addition process and subsequent reaction process. After the reaction is completed, filter and repeatedly wash with distilled water to obtain a composite powder of copper sulfide and sulfonated polyetheretherketone CuS / SPEEK, which is then dried in a vacuum drying oven at 60°C and set aside for use in preparing the surface layer of the bionic joint material.

[0054] The preparation process of the composite powder of graphene oxide and sulfonated polyetheretherketone is as follows:

[0055] To a 98wt% concentrated sulfuric acid solution, 60g of polyetheretherketone (PEEK) and 5g of graphene oxide (GO) composite powder were added while stirring the solution at room temperature. After the PEEK and GO were completely added, stirring was continued for 10 minutes. The mixture was then filtered and repeatedly washed with distilled water to obtain a GO / SPEEK composite powder of GO and sulfonated PEEK. The GO / SPEEK was then dried in a vacuum oven at 60°C and used to prepare the intermediate transition layer of the biomimetic joint material. The weight ratio of the GO / PEEK mixed powder to the concentrated sulfuric acid was 1:2.5.

[0056] The preparation process of composite powder of carbon fiber and polyetheretherketone is as follows:

[0057] A1. Add 25 g of carbon fiber to a mixed solution of concentrated nitric acid and concentrated sulfuric acid (the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 3:1), wherein the concentration of concentrated nitric acid is 67 wt % and the concentration of concentrated sulfuric acid is 98 wt % so that the mixed solution completely immerses the carbon fiber. Then, raise the temperature to 70°C and reflux while stirring. Continue stirring for 60 min, filter, and repeatedly wash the carbon fiber with distilled water. Then, dry it in a vacuum drying oven at 60°C to obtain the modified carbon fiber, which is set aside.

[0058] A2. Take 60 g of PEEK powder and 20 g of modified carbon fiber prepared in step A1 and mechanically mix them in a ball mill to prepare a mixed powder of modified carbon fiber and sulfonated polyetheretherketone, which is set aside for use in preparing the bottom layer (wear-resistant layer) of artificial joint material.

[0059] Step 3: hot-pressing the composite powder of copper sulfide and sulfonated polyetheretherketone, the composite powder of graphene oxide and sulfonated polyetheretherketone, and the composite powder of carbon fiber and polyetheretherketone obtained in step 2 and then cooling them to room temperature to obtain an antibacterial / bioactive multifunctional joint material. The process is as follows:

[0060] First, composite powders of copper sulfide and sulfonated polyetheretherketone, composite powders of graphene oxide and sulfonated polyetheretherketone, and composite powders of carbon fiber and polyetheretherketone are filled into a stainless steel mold.

[0061] The stainless steel mold was then hot-pressed in a vacuum hot-pressing furnace at a temperature of 350°C, a pressure of 12 MPa, and a holding time of 20 minutes. After hot-pressing, the mold was demolded when the temperature dropped to 100°C and cooled to room temperature, yielding a multifunctional joint material with antibacterial and bioactive properties. Example 3

[0062] This embodiment discloses a method for preparing the multifunctional joint material with antibacterial / bioactivity described in Example 1, comprising the following steps:

[0063] Step 1: Prepare sulfonated polyetheretherketone powder using concentrated sulfuric acid solution and polyetheretherketone as raw materials, and the process is as follows:

[0064] A concentrated sulfuric acid solution with a concentration of 96 wt% was taken, and 90 g of polyetheretherketone (PEEK) powder was added to the concentrated sulfuric acid solution at room temperature while stirring the concentrated sulfuric acid solution so that the concentrated sulfuric acid submerged the polyetheretherketone powder. After all the polyetheretherketone powder was added, stirring was continued at room temperature for 15 minutes, and then the solution was filtered and repeatedly washed with distilled water to remove the concentrated sulfuric acid to obtain sulfonated polyetheretherketone (SPEEK) powder. The SPEEK powder was then dried in a vacuum drying oven at 60°C for later use.

[0065] Step 2: Prepare composite powders of copper sulfide and sulfonated polyetheretherketone, composite powders of graphene oxide and sulfonated polyetheretherketone, and composite powders of carbon fiber and sulfonated polyetheretherketone.

[0066] The preparation process of the composite powder of copper sulfide and sulfonated polyetheretherketone is as follows:

[0067] S1. 30 g of the SPEEK powder prepared in step 1 was added to 100 ml of deionized water and mechanically stirred for 45 min to prepare a SPEEK suspension. Subsequently, 2.81 g of copper chloride as a soluble copper salt was added to the SPEEK suspension under mechanical stirring to prepare a SPEEK suspension containing copper ions.

[0068] S2. Add 2.20 g of thioacetamide as a soluble sulfur source to 100 ml of distilled water and stir magnetically at room temperature to fully dissolve it to prepare a sodium sulfide solution for standby use;

[0069] S3. Slowly add the thioacetamide solution prepared in step S2 to the SPEEK suspension containing copper ions prepared in step S1, and maintain mechanical stirring at the same time, so that the sodium sulfide solution reacts with the copper ions to generate CuS particles in situ in the SPEEK suspension; after the addition is completed, continue the reaction for 90 minutes while stirring to fully react. The reaction temperature is maintained at 70°C throughout the entire addition process and subsequent reaction process. After the reaction is completed, filter and repeatedly wash with distilled water to obtain a composite powder CuS / SPEEK of copper sulfide and sulfonated polyetheretherketone, which is then dried in a vacuum drying oven at 60°C and used for preparing the surface layer of the bionic joint material.

[0070] The preparation process of the composite powder of graphene oxide and sulfonated polyetheretherketone is as follows:

[0071] To a 96wt% concentrated sulfuric acid solution, 50g of polyetheretherketone (PEEK) and 2g of graphene oxide (GO) composite powder were added while stirring the solution at room temperature. After the PEEK and GO were completely added, stirring was continued for 15 minutes. The mixture was then filtered and repeatedly washed with distilled water to obtain a GO / SPEEK composite powder of GO and sulfonated PEEK. The GO / SPEEK was then dried in a vacuum oven at 60°C and used to prepare the intermediate transition layer of the biomimetic joint material. The weight ratio of the GO / PEEK mixed powder to the concentrated sulfuric acid was 1:2.

[0072] The preparation process of the composite powder of carbon fiber and sulfonated polyetheretherketone is as follows:

[0073] A1. Add 15 g of carbon fiber to a mixed solution of concentrated nitric acid and concentrated sulfuric acid (the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 3:1), wherein the concentration of concentrated nitric acid is 67 wt % and the concentration of concentrated sulfuric acid is 96 wt % so that the mixed solution completely immerses the carbon fiber. Then, raise the temperature to 70°C and reflux while stirring. Continue stirring for 90 min, filter, and repeatedly wash the carbon fiber with distilled water. Then, dry it in a vacuum drying oven at 60°C to obtain the modified carbon fiber, which is set aside.

[0074] A2. Take 60 g of PEEK powder and 15 g of modified carbon fiber prepared in step A1 and mechanically mix them in a ball mill to prepare a mixed powder of modified carbon fiber and sulfonated polyetheretherketone, which is set aside for preparing the bottom layer (wear-resistant layer) of artificial joint material.

[0075] Step 3: hot-pressing the composite powder of copper sulfide and sulfonated polyetheretherketone, the composite powder of graphene oxide and sulfonated polyetheretherketone, and the composite powder of modified carbon fiber and polyetheretherketone obtained in step 2 and then cooling them to room temperature to obtain an antibacterial / bioactive multifunctional joint material. The process is as follows:

[0076] First, composite powders of copper sulfide and sulfonated polyetheretherketone, composite powders of graphene oxide and sulfonated polyetheretherketone, and composite powders of modified carbon fiber and polyetheretherketone are filled into a stainless steel mold.

[0077] The stainless steel mold was then hot-pressed in a vacuum hot-pressing furnace at a temperature of 340°C, a pressure of 10 MPa, and a holding time of 25 minutes. After hot-pressing, the mold was demolded when the temperature dropped to 100°C and cooled to room temperature, yielding a multifunctional joint material with antibacterial and bioactive properties.

[0078] like Figure 2 The results of the antibacterial zone of Example 2 and Example 3 are shown. Figure 2It can be seen that the prepared multifunctional artificial joint material has a good antibacterial effect on Escherichia coli and Staphylococcus aureus, and the antibacterial effect is significantly enhanced with the increase of CuS content.

[0079] like Figure 3 The antibacterial effect obtained by the colony counting method of Example 2 and Example 3 is shown. Figure 3 It can be seen that the antibacterial rate of the prepared multifunctional artificial joint material against Escherichia coli and Staphylococcus aureus reached more than 90%, indicating that it has good antibacterial effect.

[0080] like Figure 4 Shown is the surface micromorphology (SEM) of hydroxyapatite (bioactivity evaluation) grown on the surface of the multifunctional artificial joint material before and after immersion in simulated body fluid. Figure 4 (a) is the surface morphology without immersion. Figure 4 (b) is the surface micromorphology after immersion in simulated body fluid for 9 days. Figure 4 It can be seen that after the multifunctional artificial joint material was immersed in simulated body fluid for 9 days, a dense hydroxyapatite layer was deposited on its surface, indicating that it has excellent biological activity.

[0081] The preferred embodiments of the present invention are described in detail above with reference to the accompanying drawings. The embodiments described in the present invention are merely descriptions of the preferred embodiments of the present invention and do not limit the concept and scope of the present invention. The various specific technical features described in the above specific embodiments can be combined in any suitable manner unless there is any contradiction. Such combinations should also be regarded as disclosed in the present invention as long as they do not violate the concept of the present invention. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0082] The present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention and without departing from the design concept of the present invention, various modifications and improvements made to the technical solution of the present invention by those skilled in the art should fall within the scope of protection of the present invention. The technical contents for which protection is sought in the present invention have been fully recorded in the claims.

Claims

1. A multifunctional artificial joint material with antibacterial / bioactive properties, characterized in that: The invention comprises an antibacterial / bioactive layer, a mechanical performance enhancing layer, and a wear-resistant layer. The antibacterial / bioactive layer, the mechanical performance enhancing layer, and the wear-resistant layer are stacked to form a three-layer stacked structure, wherein the mechanical performance enhancing layer serves as the middle layer of the three-layer stacked structure. The material of the antibacterial / bioactive layer is a copper sulfide / sulfonated polyetheretherketone composite material, the material of the mechanical performance enhancing layer is a graphene oxide / sulfonated polyetheretherketone composite material, and the material of the wear-resistant layer is a modified carbon fiber / polyetheretherketone composite material.

2. The multifunctional artificial joint material with antibacterial / biological activity according to claim 1, characterized in that: In the copper sulfide / sulfonated polyetheretherketone composite material used as the antibacterial / bioactive layer material, the mass ratio of copper sulfide to sulfonated polyetheretherketone is 1:50~1:

10.

3. The multifunctional artificial joint material with antibacterial / biological activity according to claim 1, characterized in that: In the graphene oxide / sulfonated polyetheretherketone composite material used as the mechanical property enhancement layer material, the mass ratio of graphene oxide to sulfonated polyetheretherketone is 1:100~1:

10.

4. The multifunctional artificial joint material with antibacterial / biological activity according to claim 1, characterized in that: In the modified carbon fiber / polyetheretherketone composite material used as the wear-resistant layer material, the mass ratio of carbon fiber to polyetheretherketone is 1:10~1:

2.

5. A method for preparing a multifunctional joint material with antibacterial / biological activity according to any one of claims 1 to 4, characterized in that: The following steps are involved: Step 1, preparing sulfonated polyetheretherketone powder using concentrated sulfuric acid solution and polyetheretherketone as raw materials; Step 2: Using a soluble copper salt, a soluble sulfur source solution, and the sulfonated polyetheretherketone powder prepared in step 1 as raw materials, a composite powder of copper sulfide and sulfonated polyetheretherketone is prepared; Composite powder of graphene oxide and sulfonated polyetheretherketone was prepared using graphene oxide, concentrated sulfuric acid solution and polyetheretherketone powder as raw materials. A composite powder of modified carbon fiber and polyetheretherketone is prepared using carbon fiber, a mixed solution of concentrated nitric acid / concentrated sulfuric acid, and polyetheretherketone powder as raw materials; Step 3. Hot-press the composite powder of copper sulfide and sulfonated polyetheretherketone, the composite powder of graphene oxide and sulfonated polyetheretherketone, and the composite powder of modified carbon fiber and polyetheretherketone obtained in step 2 and then cool them to room temperature to obtain an antibacterial / bioactive multifunctional joint material; wherein the hot pressing temperature during hot pressing is 320~380°C, the pressure is 10~15MPa, and the holding time is 20~30 min.

6. The preparation method according to claim 5, characterized in that Step 1 process is as follows: Taking concentrated sulfuric acid with a concentration of 95-98 wt%, adding polyetheretherketone powder to the concentrated sulfuric acid solution while stirring the concentrated sulfuric acid solution at room temperature, wherein the mass ratio of polyetheretherketone to concentrated sulfuric acid solution is 1:2-1:3; After all the polyetheretherketone is added, stirring is continued for 5 to 20 minutes, and then the mixture is filtered and washed to obtain sulfonated polyetheretherketone powder.

7. The preparation method according to claim 5, characterized in that The preparation process of the composite powder of copper sulfide and sulfonated polyetheretherketone in step 2 is as follows: First, the sulfonated polyetheretherketone prepared in step 1 is prepared into a suspension, and then a soluble copper salt is added to the suspension to obtain a sulfonated polyetheretherketone suspension containing copper ions; Next, a soluble sulfur source solution is prepared; Finally, the soluble sulfur source solution is added dropwise to the sulfonated polyetheretherketone suspension containing copper ions at a temperature of 60-80°C, and then stirred and reacted at a temperature of 60-80°C for 60-120 minutes. After the reaction is completed, the composite powder of copper sulfide and sulfonated polyetheretherketone is obtained after filtering and washing. The molar ratio of copper ions in the soluble copper salt and sulfur ions in the soluble sulfur source solution is 1:1-1:1.5, and the mass ratio of the generated CuS to sulfonated polyetheretherketone is 1:50-1:

10.

8. The preparation method according to claim 5, characterized in that The preparation process of the composite powder of graphene oxide and sulfonated polyetheretherketone in step 2 is as follows: Taking concentrated sulfuric acid with a concentration of 95-98 wt%, adding graphene oxide and polyetheretherketone to the concentrated sulfuric acid solution while stirring the concentrated sulfuric acid solution at room temperature, continuing to stir for 5-20 minutes after all the graphene oxide and polyetheretherketone powders are added, and then filtering and washing to obtain a composite powder of graphene oxide and sulfonated polyetheretherketone; The mass ratio of the graphene oxide and polyetheretherketone mixed powder to concentrated sulfuric acid is 1:2~1:

3.

9. The preparation method according to claim 5, characterized in that The preparation process of the composite powder of modified carbon fiber and polyetheretherketone in step 2 is as follows: The polyetheretherketone powder and the modified carbon fiber are stirred and mixed to obtain a composite powder of the modified carbon fiber and the polyetheretherketone; The modified carbon fiber is obtained by modifying a mixed solution formed by concentrated nitric acid with a concentration of 65-68wt% and concentrated sulfuric acid with a concentration of 95-98wt%, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 3:1, and the mass dosage ratio of the mixed solution to the carbon fiber is 1:2-1:3.

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