Method and system for preparing hydroxyapatite coating by compounding laser induction and hydrothermal synthesis on surface of polyaryletherketone

Abstract

The invention relates to the technical field of preparation of polyaryletherketone coatings, in particular to a method and a system for preparing a hydroxyapatite coating by compounding laser induction and hydrothermal synthesis on the surface of polyaryletherketone. The method comprises the following steps: immersing a polyether-ether-ketone material into a calcium-phosphorus solution, irradiating the surface of the polyether-ether-ketone material by using laser, so that the surface of the polyether-ether-ketone material is slightly melted, the slightly melted part of the surface of the polyether-ether-ketone material reacts with calcium ions in the calcium-phosphorus solution to generate a composite coating, and heating the calcium-phosphorus solution to form the composite coating. And depositing a hydroxyapatite coating on the surface of the composite coating through a hydrothermal synthesis method. According to the method, the surface is subjected to micro melting through laser irradiation and reacts with calcium ions to generate the composite coating, the bonding strength between the polyether-ether-ketone material and the coating is enhanced in the process, the thickness and uniformity of the coating can be accurately controlled by adjusting laser parameters and hydrothermal synthesis conditions, and the method integrates the laser technology and the hydrothermal synthesis technology and is suitable for large-scale production. The technological process is simple and feasible, and large-scale production and application are facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of polyaryletherketone coating preparation, and in particular to a method and system for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone. Background Art

[0002] Polyetheretherketone (PEEK) is a high-temperature thermoplastic polymer. Due to its good biocompatibility, radiopacity, and mechanical strength similar to natural bone, extensive research and applications have been carried out in the fields of orthopedics, spine, and trauma implant materials. Although PEEK materials have significant advantages in the field of implant materials, the biological inertness of their surfaces leads to the easy formation of a fibrous capsule layer at the interface between PEEK implants and host bone, affecting their bone integration and osteogenic activity, and thus affecting the use effect of the implants. Currently, there are mainly two methods to improve the bone integration and osteogenic activity of PEEK materials. One is to change the surface morphology and chemical properties of PEEK materials through surface modification, thereby promoting the bone integration ability of the materials. The other is to deposit active materials on the surface of PEEK materials to form a bioactive coating.

[0003] Hydroxyapatite (HA) has a calcium-phosphorus ratio similar to that of human bone and has good biocompatibility and osteoconductivity. Currently, the mainstream method for surface coating modification of PEEK is to deposit a hydroxyapatite coating on the surface of PEEK materials, forming a multifunctional coating interface on its surface, endowing PEEK with biological functionality, and enhancing the compatibility between the material and the organism. Although depositing a hydroxyapatite coating on the surface of PEEK materials can effectively improve the bone integration ability, the hydroxyapatite coating deposited on the surface of PEEK materials often has poor adhesion to the substrate, resulting in a decrease in the mechanical properties of the material, and thus may shorten the lifespan of the implant.

[0004] Currently, the main manufacturing processes for hydroxyapatite coatings are as follows: plasma spraying method, ion beam deposition method, laser cladding method, electrochemical deposition method, hydrothermal synthesis method, etc.; however, high temperatures during the preparation processes of methods such as plasma spraying method, ion beam deposition method, and laser cladding method may cause serious thermal deformation and other problems of PEEK implants; the incubation time required for forming a hydroxyapatite coating on the surface of PEEK by electrochemical deposition method and hydrothermal synthesis method is relatively long, and the thickness of the hydroxyapatite coating formed on the surface of PEEK materials is uneven, and the mechanical bonding property is poor. Summary of the Invention

[0005] In order to solve the problem of low deposition efficiency of hydroxyapatite coatings on PEEK materials, and at the same time reduce the deformation and damage of PEEK materials during the reaction, the present invention provides a method and system for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone.

[0006] On the one hand, a method for preparing a hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone provided by the present invention adopts the following technical scheme: A method for preparing a hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone, comprising the following preparation steps: Immerse the polyetheretherketone material in a calcium phosphate solution; Use laser irradiation on the surface of the polyetheretherketone material to cause micro-melting on the surface of the polyetheretherketone material; The micro-melted part on the surface of the polyetheretherketone material reacts with calcium ions in the calcium phosphate solution to form a composite coating; Heat the calcium phosphate solution, and deposit a hydroxyapatite coating on the surface of the composite coating by hydrothermal synthesis method.

[0007] Through laser irradiation, the surface is micro-melted and reacts with calcium ions to form a composite coating. In this process, the bonding strength between the polyetheretherketone material and the coating is enhanced. Hydroxyapatite is a bioactive material that can promote the adhesion and growth of bone cells, improve the biocompatibility and bone integration ability of the implant material. The existence of the composite coating can effectively protect the substrate material, reduce corrosion in the body fluid environment, improve the durability and service life of the material. By adjusting the laser parameters and hydrothermal synthesis conditions, the thickness and uniformity of the coating can be precisely controlled, so as to meet the requirements of different applications. This method integrates laser technology and hydrothermal synthesis technology, and the process flow is simple and easy to implement, facilitating large-scale production and application.

[0008] Further, the calcium phosphate solution is prepared, including adjusting the concentration and pH value of the calcium phosphate solution.

[0009] By precisely adjusting the concentration of the calcium phosphate solution, the composition and structure of the generated composite coating can be controlled, thereby affecting the denseness, uniformity and stability of the coating, improving the overall performance of the coating. Appropriately adjusting the pH value can promote the rapid and stable deposition of hydroxyapatite, ensure the high quality and uniformity of the coating. Adjusting the concentration and pH value of the calcium phosphate solution can control the crystallization degree of hydroxyapatite in the coating, thereby improving the bioactivity of the coating, promoting the adhesion and growth of bone cells, and enhancing the biocompatibility of the material. By precisely adjusting the pH and concentration of the solution, excessive by-products or ineffective reactions can be avoided during the coating formation process, and the purity and functionality of the material surface coating can be improved.

[0010] Further, while heating the calcium phosphate solution for hydrothermal synthesis, continuously use laser irradiation to induce the deposition of a hydroxyapatite coating on the surface of the polyetheretherketone material.

[0011] Laser irradiation provides additional energy to promote the reaction, accelerating the deposition process of hydroxyapatite on the surface of polyetheretherketone, thereby shortening the preparation time and improving production efficiency. Laser irradiation causes micro-melting on the material surface, which helps to improve the interfacial bonding force between the hydroxyapatite coating and the polyetheretherketone substrate, ensuring the stability and durability of the coating. The synergistic effect of laser induction and hydrothermal synthesis can optimize the microstructure of the coating, making it dense and crack-free, thus enhancing the mechanical properties and corrosion resistance of the coating.

[0012] Furthermore, the laser irradiation induction and hydrothermal synthesis are carried out in one cycle or multiple cycles when processing polyetheretherketone materials.

[0013] Through multiple cycles, the synergistic effect of laser irradiation and hydrothermal synthesis can gradually improve the quality of the coating. Each cycle helps to enhance the denseness, uniformity and stability of the coating, avoiding coating defects or non-uniformities, thus achieving higher coating quality. Multiple cycles help to enhance the bonding force between the coating and the polyetheretherketone substrate. Each laser irradiation and hydrothermal treatment can promote the change of the surface microstructure of the material, enhance the adhesion of the coating, and reduce the risk of coating peeling or delamination. By carrying out multiple cycles, the thickness and morphology of the coating can be precisely controlled, ensuring good fusion between each coating layer and avoiding performance non-uniformities caused by too thick or too thin coatings.

[0014] Furthermore, before using laser irradiation, adjust the parameters of the laser used for laser irradiation, including pulse width, wavelength, frequency and energy.

[0015] Improve the deposition rate and uniformity of the coating. Optimized laser parameters can accelerate coating deposition and ensure the uniformity of the coating in different regions, enhance the bonding force between the coating and the substrate. Precisely controlling the laser parameters can improve the microstructure and surface energy of the coating, enhance the adhesion of the coating, improve the mechanical properties and durability of the coating. The optimized coating microstructure can significantly enhance its hardness, wear resistance and corrosion resistance, and enhance the bioactivity and compatibility of the coating.

[0016] Furthermore, the light source of the laser includes infrared light and green light.

[0017] Infrared light is used for deep thermal effect treatment to enhance the bonding force and mechanical properties between the coating and the substrate. Green light is used for surface fine processing to optimize the surface microstructure and bioactivity. The combined use of infrared light and green light can maximize the advantages of each, comprehensively enhancing the mechanical properties, bioactivity, durability and adhesion of the coating.

[0018] Furthermore, before using laser irradiation, adjust the laser irradiation path, and the irradiation path is planned according to the designed coating area and shape.

[0019] By precisely planning the laser irradiation path, coating deposition can be carried out in a pre-designed shape and area to meet specific application requirements. By optimizing the irradiation path, laser treatment can be performed only in the required areas, reducing material waste and improving material utilization rate. Precisely planning the laser irradiation path can ensure uniform distribution of laser energy throughout the coating area, avoiding local overheating or insufficient energy, and ensuring the consistency of coating thickness and performance. By optimizing the irradiation path, edge effects can be reduced, avoiding the phenomenon of too thick or too thin coating edges, and ensuring the uniformity and integrity of the entire coating.

[0020] On the other hand, a system for preparing hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone provided by the present invention adopts the following technical solutions: A system for preparing hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone, comprising a laser generator and a reaction vessel. The laser generator is connected with a scanning galvanometer, and the scanning galvanometer is controlled to be movably arranged directly above the reaction vessel and emit a laser beam towards the reaction vessel. The laser generator and the scanning galvanometer are connected to a control system through control wires.

[0021] By controlling the movement of the laser beam, the scanning galvanometer can achieve precise laser irradiation of a specific area, ensuring that the coating can be uniformly formed within the designed area. The control system can adjust the path of the scanning galvanometer according to real-time feedback to adapt to different coating shape and area requirements, ensuring the accuracy and consistency of the coating. The scanning galvanometer can evenly distribute laser energy according to a preset path, avoiding local overheating or insufficient energy, and ensuring the uniformity of coating thickness and quality.

[0022] Furthermore, a fixing component is arranged at the bottom of the reaction vessel for fixing the polyetheretherketone substrate.

[0023] The fixing component can firmly fix the PEEK substrate, preventing the substrate from moving or vibrating during laser irradiation and hydrothermal synthesis, ensuring the stability and safety of the processing process. The fixing component can prevent the substrate from falling off or tilting during the processing process, avoiding uneven laser irradiation and coating defects caused by changes in the position of the substrate.

[0024] Furthermore, the method for preparing hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone as described above is used for operation.

[0025] In summary, the present invention has the following beneficial technical effects: 1. The surface is micro-melted by laser irradiation and reacts with calcium ions to form a composite coating. During this process, the bonding strength between the polyetheretherketone material and the coating is enhanced. Hydroxyapatite is a bioactive material that can promote the adhesion and growth of bone cells, improving the biocompatibility and bone integration ability of the implant material. The presence of the composite coating can effectively protect the substrate material, reduce corrosion in the body fluid environment, and improve the durability and service life of the material. By adjusting the laser parameters and hydrothermal synthesis conditions, the thickness and uniformity of the coating can be precisely controlled to meet the requirements of different applications. This method integrates laser technology and hydrothermal synthesis technology, and the process flow is simple and easy to implement, facilitating large-scale production and application.

[0026] 2. By optimizing the preparation of the solution concentration and pH value, it helps to achieve precise control of the coating properties and improve the performance and quality of the final product. By continuously using laser irradiation during the hydrothermal synthesis process, the deposition efficiency and quality of the hydroxyapatite coating can be significantly improved, providing a more effective approach for preparing high-performance and bioactive coatings.

[0027] 3. By implementing multiple cycles of laser irradiation and hydrothermal synthesis, the overall performance of the hydroxyapatite coating can be significantly improved, ensuring that it has better bioactivity, mechanical properties, adhesion, and durability, and can meet the requirements of different applications, achieving fine control, improving the consistency and stability of the coating, and providing guarantee for the long-term application of the material.

[0028] 4. By optimizing the pulse width, wavelength, frequency, and energy of the laser, the effect of laser irradiation-induced and hydrothermal synthesis in treating polyetheretherketone materials can be significantly improved, ensuring the high quality and high performance of the hydroxyapatite coating and meeting various application requirements. Using infrared light and green light as the laser irradiation light source, by adjusting its parameters, the deposition effect of the hydroxyapatite coating on the surface of polyetheretherketone materials can be significantly improved. This method can not only optimize the overall performance of the coating but also achieve efficient and high-quality coating deposition, meeting various application requirements in the field of biomaterials.

[0029] 5. By adjusting the laser irradiation path before laser irradiation and planning according to the designed coating area and shape, the deposition effect of the hydroxyapatite coating on the surface of polyetheretherketone materials can be significantly improved. This method can not only improve the uniformity and adhesion of the coating but also optimize the microstructure and mechanical properties of the coating, meeting the requirements of various applications. In addition, precise path planning can also improve the processing efficiency, reduce material waste, and enhance the economy and sustainability of the overall production.

[0030] 6. This system for preparing hydroxyapatite coatings on the surface of polyaryletherketone by laser induction and hydrothermal synthesis realizes efficient, precise, and controllable coating preparation through the coordinated work of a laser generator, a scanning galvanometer, and a control system. It significantly improves the quality, performance, and production efficiency of the coatings. The design of adding a fixing component at the bottom of the reaction vessel to fix the PEEK substrate significantly enhances the stability, precision, and efficiency of the coating preparation process, ensures the uniformity and quality of the coatings, improves the adhesion and durability of the coatings, and enhances the versatility and adaptability of the system. This provides an important guarantee for the efficient, stable, and controllable preparation of hydroxyapatite coatings. Description of the Drawings

[0031] Figure 1 It is a flowchart of the steps for preparing hydroxyapatite coatings in the present invention; Figure 2 It is a schematic diagram of the composite preparation of hydroxyapatite coatings in the present invention; Figure 3 It is an effect diagram of the preparation of hydroxyapatite coatings in the present invention; Figure 4 It is a grayscale image of the undulating scan of the preparation of hydroxyapatite coatings in the present invention; Figure 5 It is a statistical chart of the undulating scan of the preparation of hydroxyapatite coatings in the present invention; Figure 6 It is a schematic diagram of the system connection of the processing device in the present invention.

[0032] Description of the Reference Numerals: 1. Laser generator, 2. Reaction vessel, 3. Scanning galvanometer, 4. Control system; A is calcium phosphate solution, B is polyaryletherketone substrate, C is hydroxyapatite coating, D is laser beam, E is polyaryletherketone molten pool and melting area. Detailed Embodiments

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the attached Figures 1-6 , and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present invention.

[0035] Example 1: The embodiment of the present invention discloses a method for preparing a hydroxyapatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone. Referring to Figures 1-5 , it includes the following preparation steps: Immerse the polyetheretherketone material in the calcium phosphate solution; Use laser irradiation on the surface of the polyetheretherketone material to cause micro-melting on the surface of the polyetheretherketone material; The micro-melted part on the surface of the polyetheretherketone material reacts with calcium ions in the calcium phosphate solution to generate a composite coating; Heat the calcium phosphate solution, and deposit a hydroxyapatite coating on the surface of the composite coating by hydrothermal synthesis method.

[0036] The ratio of the calcium phosphate solution is as follows: prepare mixture 1 by mixing phosphoric acid and DMEM cell culture medium at a ratio of 1:14, prepare mixture 2 by mixing calcium chloride and DMEM cell culture medium at a ratio of 1:9, and the ratio of mixture 1: mixture 2: DMEM cell culture medium is 1:5:13 to prepare the calcium phosphate solution. At the same time, add a certain amount of NaOH solution to adjust the pH of the calcium phosphate solution to make it alkaline.

[0037] Use the light source formed by a laser with a wavelength of 1064 nm and a pulse width of 70 ns as the light source for laser-induced and hydrothermal synthesis of the apatite coating.

[0038] The processing parameters are as follows: laser power is 10 - 100 W, scanning speed is 10 - 1000 mm / s, defocus amount is 0 - 5 mm, and the number of processing times is 1 - 500 times.

[0039] Clean the surface of the PEEK material, immerse it in the calcium phosphate solution with the adjusted pH value, select the processing area, plan the laser scanning path, and use a scanning galvanometer to prepare the apatite coating by laser-induced and hydrothermal synthesis on the surface of the PEEK material.

[0040] After completion, turn off all equipment to complete the process of preparing the apatite coating by laser-induced and hydrothermal synthesis on the surface of polyaryletherketone.

[0041] Example 2: Based on Example 1, add: Referring to Figures 1-5, prepare a calcium phosphate solution, including adjusting the concentration and pH value of the calcium phosphate solution.

[0042] While heating the calcium phosphate solution for hydrothermal synthesis, continuously use laser irradiation to induce the deposition of hydroxyapatite coating on the surface of the polyetheretherketone material.

[0043] The laser irradiation induction and hydrothermal synthesis are carried out in one cycle or multiple cycles when processing the polyetheretherketone material.

[0044] The laser-induced treatment process refers to irradiating the PEEK material immersed in the calcium phosphate solution with laser, melting the surface material and reacting with calcium ions to generate a composite coating, etc.

[0045] The laser hydrothermal synthesis reaction refers to irradiating a specific area of the calcium phosphate solution with laser, rapidly increasing the temperature of the solution in this area, causing calcium ions to precipitate and adhere to the surface of the composite coating, and the preparation of hydroxyapatite coatings with arbitrary areas and patterns can be achieved through laser path planning.

[0046] By changing the laser processing conditions, the preparation process and coating thickness of the hydroxyapatite coating can be quantitatively adjusted. By changing the laser scanning path, the preparation of hydroxyapatite coatings in arbitrary areas can be achieved.

[0047] Example 3: Based on Example 1, add: Refer to Figures 1-5 , before using laser irradiation, adjust the parameters of the laser for laser irradiation, including pulse width, wavelength, frequency and energy.

[0048] The light source of the laser includes infrared light and green light.

[0049] Before using laser irradiation, adjust the laser irradiation path, and the irradiation path is planned according to the designed coating area and shape.

[0050] By optimizing the process parameters, an apatite coating can be prepared on the surface of the PEEK material through the combination of laser induction and hydrothermal synthesis. The coating thickness can reach 50 μm, and the coating deposition efficiency can reach 2.5 mm3 / min. The preparation of coatings with specific areas and thicknesses can be achieved, and the efficiency is significantly improved compared with other deposition methods.

[0051] By simultaneously reacting the surface material of the PEEK with the calcium phosphate solution through laser cladding to produce a composite coating, the bonding strength between the hydroxyapatite coating and the surface of the substrate material is significantly enhanced.

[0052] Example 4: This embodiment of the present invention discloses a system for preparing a hydroxyapatite coating on the surface of polyaryletherketone by combining laser induction and hydrothermal synthesis. Refer to Figure 6, including a laser generator 1 and a reaction container 2. The laser generator 1 is connected to a scanning galvanometer 3. The scanning galvanometer 3 is controlled to move and be arranged directly above the reaction container 2 and emit a laser beam towards the reaction container 2. The laser generator 1 and the scanning galvanometer 3 are connected to a control system 4 through control wires.

[0053] A fixing component is arranged at the bottom of the reaction container 2 for fixing the polyetheretherketone substrate.

[0054] Use and operate according to the method for preparing a hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of a polyaryletherketone as described in Examples 1-3.

[0055] At the same time, there are also motion control and other auxiliary parts, which can realize the preparation of a composite coating on the surface of PEEK material and the efficient deposition of hydroxyapatite coating. While reducing the deformation and damage of PEEK material, the preparation efficiency of hydroxyapatite coating can be further improved.

[0056] The above content is only an example and explanation of the structure of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as it does not deviate from the scope defined by the structure of the invention, it shall fall within the protection scope of the present invention.

Claims

1. A method for preparing hydroxyapatite coating on the surface of polyaryletherketone by laser induction and hydrothermal synthesis, characterized in that: The method comprises the following preparation steps: immersing the polyetheretherketone material in a calcium-phosphate solution; Using laser to irradiate the surface of the polyetheretherketone material, so that the surface of the polyetheretherketone material is slightly melted; The slightly melted part of the surface of the polyetheretherketone material reacts with the calcium ions in the calcium-phosphorus solution to form a composite coating; The calcium-phosphorus solution is heated to deposit a hydroxyapatite coating on the surface of the composite coating by a hydrothermal synthesis method.

2. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 1, characterized in that: The calcium-phosphate solution is prepared, including adjusting the concentration and pH value of the calcium-phosphate solution.

3. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 1, characterized in that: The calcium phosphate solution is heated for hydrothermal synthesis while laser irradiation is continuously used to induce deposition of a hydroxyapatite coating on the surface of the polyetheretherketone material.

4. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 3, characterized in that: The laser irradiation induction and hydrothermal synthesis are carried out in one cycle or multiple cycles when treating the polyetheretherketone material.

5. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 1, characterized in that: Before using laser irradiation, adjust the parameters of the laser used for laser irradiation, including pulse width, wavelength, frequency and energy.

6. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 5, characterized in that: The light source of the laser includes infrared light and green light.

7. The method for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 1, characterized in that: Before using laser irradiation, the laser irradiation path is adjusted, and the irradiation path is planned according to the designed coating area and shape.

8. A system for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of poly(aryletherketone), characterized in that: The invention comprises a laser generator (1) and a generating container (2), wherein the laser generator (1) is connected to a scanning galvanometer (3), wherein the scanning galvanometer (3) is controlled to move and is arranged directly above the generating container (2) and emits a laser beam toward the generating container (2), and the laser generator (1) and the scanning galvanometer (3) are connected to a control system (4) via a control wire.

9. The system for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 8, characterized in that: A fixing component is arranged at the bottom of the generating container (2) for fixing the polyetheretherketone matrix.

10. The system for preparing hydroxyapatite coating by laser induction and hydrothermal synthesis on the surface of polyaryletherketone according to claim 8, characterized in that: The method for preparing hydroxyapatite coating by composite laser induction and hydrothermal synthesis on the surface of polyaryletherketone as described in any one of claims 1 to 7 is used and operated.

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