Nano silicon-graphene synergistically enhanced zinc-based bone implant and preparation method thereof

Abstract

The invention discloses a preparation method of a nano silicon-graphene synergistically enhanced zinc-based bone implant. The preparation method comprises the following operation steps: S1, preparing a stable graphene oxide suspension; s2, preparing a silicon suspension; s3, preparing graphene oxide-nano silicon mixed powder, and performing thermal reduction reaction to obtain graphene-silicon carbide-nano silicon composite powder; s4, zinc / graphene-silicon carbide-nano silicon mixed powder is prepared; s5, taking the zinc / graphene-silicon carbide-nano silicon mixed powder as a raw material, and preparing the zinc-based bone implant by adopting a selective laser melting process in a protective atmosphere; the invention also provides the zinc-based bone implant prepared by adopting the preparation method. According to the invention, the mechanical property of the zinc-based bone implant can be obviously improved, and the prepared zinc-based bone implant has excellent biological activity.

Description

Technical Field

[0001] The present invention relates to the technical field of the design and preparation of biomedical implants, and particularly to a zinc-based bone implant synergistically reinforced by nano-silicon and graphene and a preparation method thereof. Background Art

[0002] In recent years, with the increase in population aging and the development of industries such as industry, transportation, and sports, the demand for artificial bone implants has been continuously increasing. Therefore, it is urgent to develop ideal bone implants to meet clinical needs.

[0003] As a biodegradable metal, zinc has good biocompatibility and a moderate degradation rate. After being implanted into the body, it can be gradually degraded to avoid secondary surgery, greatly reducing the risk and burden on patients, and is becoming a research hotspot for bone implant materials. At the same time, zinc is one of the essential trace elements for the human body and plays an important role in the work and regulation of the human immune system, nervous system, and metabolic system. Many studies have shown that zinc ions can stimulate the differentiation of osteoblasts and the formation of mineralized tissues, and can also participate in inhibiting bone resorption and retaining bone mass in the human body, thereby promoting bone growth and healing. At present, domestic and foreign scholars have carried out a large number of studies on the biodegradable metal zinc, but there is still a certain gap from the requirements of clinical applications. The main obstacle is that the strength and ductility of metallic zinc are relatively poor, and it is difficult to provide effective mechanical support during the bone repair process. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a zinc-based bone implant synergistically reinforced by nano-silicon and graphene and a preparation method thereof. It uses biodegradable metal zinc as the matrix and in-situ interface-bonded nano-silicon and graphene as the reinforcing phase, and prepares the zinc-based bone implant by selective laser melting, which can significantly improve the mechanical properties of the zinc-based bone implant, and the prepared zinc-based bone implant has relatively excellent bioactivity.

[0005] The technical solution provided by the present invention is as follows: A preparation method of a zinc-based bone implant synergistically reinforced by nano-silicon and graphene, comprising the following operating steps: S1. Add a certain amount of graphene oxide to distilled water and ultrasonically disperse it for a period of time to form a stable graphene oxide suspension; S2. Pour a certain amount of silicon nano-powder into an anhydrous ethanol solution to form an ethanol solution of silicon. After ultrasonically dispersing it for a period of time, add a certain amount of aminopropyltrimethoxysilane to the above ethanol solution of silicon and stir to form a silicon suspension; S3. Slowly add the graphene oxide suspension prepared in step S1 to the silicon suspension prepared in step S2 at a certain ratio, stir evenly to form a mixed solution, and the mixed solution is centrifuged and vacuum dried in sequence to obtain graphene oxide-nano silicon mixed powder. The graphene oxide-nano silicon mixed powder is then subjected to a thermal reduction reaction to obtain a graphene-silicon carbide-nano silicon composite powder; S4. Place the graphene-silicon carbide-nano silicon composite powder and zinc powder prepared in step S3 in an absolute ethanol solution for ultrasonic dispersion in a certain mass ratio in sequence. Subsequently, wet ball milling is performed on the dispersed mixed solution, and after filtration and drying, a zinc / graphene-silicon carbide-nano silicon mixed powder is obtained; S5. Using the zinc / graphene-silicon carbide-nano silicon mixed powder prepared in step S4 as a raw material, a zinc-based bone implant is prepared by a selective laser melting process under a protective atmosphere.

[0006] Preferably, the average particle size of the silicon nano powder in step S2 is 50-200 nm.

[0007] Preferably, the volume ratio of the graphene oxide suspension to the silicon suspension in step S3 is 10:1-14:1. If the volume ratio of the graphene oxide suspension to the silicon suspension is too large, fewer silicon nanoparticles will form on the surface of the graphene sheets, and it cannot effectively promote the dispersion of graphene to avoid agglomeration. If the volume ratio of the graphene oxide suspension to the silicon suspension is too small, too much silicon powder will remain in the obtained mixed powder.

[0008] Preferably, in step S3, the graphene oxide-nano silicon mixed powder is heated to 600-800 °C and kept warm for 2-3 h for a thermal reduction reaction in an argon atmosphere in a tubular furnace. If the heat treatment time is too short, very little silicon carbide will form on the surface of the graphene, and it is easy for the graphene and the silicon nanoparticles on the surface to peel off during the ball milling process, resulting in an insignificant improvement in the dispersion of graphene in the zinc matrix and inconsistent interfacial properties. If the heat treatment time is too long, the graphene will be partially thermally degraded under the action of high temperature for a long time, resulting in excessive consumption of graphene, which will weaken the strengthening effect of graphene on the zinc matrix and is not conducive to the improvement of its mechanical properties.

[0009] Preferably, the mass ratio of the graphene-silicon carbide-nano silicon composite powder to the zinc powder in step S4 is 2:98-5:95.

[0010] Preferably, in the step S4, the ball milling speed is 250-400 r / min and the ball milling time is 2-4 h. Appropriate ball milling parameters can ensure the integrity of silicon carbide and silicon nanoparticles on the surface of graphene, and at the same time promote the dispersion of graphene-silicon carbide-nano silicon composite powder in zinc powder. When the ball milling parameters are higher than the protection scope of the present invention, the silicon nanoparticles on the surface of graphene will partially peel off, and due to the high strength and high hardness of silicon carbide, the graphene sheets in the mixed powder will be cut and deformed; when the ball milling parameters are lower than the protection scope of the present invention, the graphene-silicon carbide-nano silicon composite powder is unevenly dispersed in the zinc powder, making it difficult to achieve the ideal strengthening effect of graphene-silicon carbide-nano silicon on the zinc matrix.

[0011] Preferably, in the step S5, the power of the laser is 80-100 W, the scanning rate of the laser is 100-200 mm / s, the spot diameter of the laser is 45-55 µm, and the powder bed thickness (a standard process parameter of the SLM technology) is 0.1-0.2 mm. If the laser energy is too low, the zinc metal powder will not be fully melted, resulting in pores or even inability to form; if the laser energy is too high, the excessive temperature will cause severe balling of zinc and also damage the graphene structure, weakening the strengthening effect of graphene on the zinc metal matrix. Therefore, the power of the laser is preferably 80-100 W.

[0012] A zinc-based bone implant with nano-silicon / graphene synergistic reinforcement is prepared by using the preparation method of the zinc-based bone implant with nano-silicon / graphene synergistic reinforcement described above.

[0013] The present invention has the following advantages over the prior art: The preparation method of the nano-silicon / graphene co-reinforced zinc-based bone implant of the present invention uses graphene-silicon carbide-nano-silicon prepared by in-situ reaction as the reinforcing phase, which is compounded into metallic zinc by selective laser melting to prepare the nano-silicon / graphene co-reinforced zinc-based bone implant. Through in-situ reaction, the graphene and silicon nanoparticles form a three-dimensional point-plane binding structure, which can promote the dispersion of each other and avoid agglomeration. Moreover, the silicon nanoparticles existing on the uneven surface of the graphene (forming uniform silicon nanoparticles on the graphene surface) can greatly increase the contact area between the reinforcing phase and the zinc matrix. At the same time, the hydrolysis of silicon particles will form negatively charged silanol groups, accelerating the deposition of bone-like apatite and improving the bioactivity of the zinc-based bone implant. In addition, graphene and silicon nanoparticles form silicon carbide through in-situ reaction. On the one hand, silicon carbide can serve as an interface bridge between the graphene sheets and silicon nanoparticles, improving the interfacial bonding strength between the two; on the other hand, silicon carbide has good mechanical properties and can synergistically strengthen the metallic zinc matrix with graphene, thus significantly improving the mechanical properties of the zinc-based bone implant. In addition, silicon carbide also has good thermal stability, which can hinder the high-temperature thermal degradation of graphene during the processing, and further give full play to the strengthening effect of the graphene reinforcing phase, improving the mechanical properties of the zinc-based bone implant, which is particularly suitable for bone repair materials.

[0014] The preparation method of the nano-silicon / graphene co-reinforced zinc-based bone implant of the present invention uniformly mixes the graphene-silicon carbide-nano-silicon composite powder and zinc powder through wet ball milling. Compared with conventional mechanical ball milling, wet ball milling can avoid the structural damage of the graphene-silicon carbide-nano-silicon composite powder.

[0015] The preparation method of the nano-silicon / graphene co-reinforced zinc-based bone implant of the present invention realizes the rapid preparation of the nano-silicon / graphene co-reinforced zinc-based bone implant through a unique selective laser melting process. The optimized laser processing parameters can not only refine the zinc matrix grains and increase the number of grain boundaries through rapid heating and cooling, which is beneficial to improving the mechanical and degradation behaviors of the alloy, but more importantly, the graphene structure will not be damaged under the specific process of the present invention, which has more favorable advantages for giving full play to the strengthening effect of graphene.

[0016] In summary, through the unique powder treatment and laser processing techniques of the present invention, under the synergistic action of various process parameters, in-situ interface bonding of nano-silicon / graphene co-reinforces the zinc matrix, thereby preparing a medical zinc-based bone implant with good mechanical properties. Brief Description of the Drawings

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments described in the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can also be obtained based on these drawings.

[0018] Figure 1 SEM image of the surface of graphene after treatment in Example 1 of the present invention; Figure 2 SEM image of the nano-silicon / graphene co-reinforced zinc-based bone implant prepared in Example 1 of the present invention; Figure 3 SEM image of the surface of graphene after treatment in Example 2 of the present invention; Figure 4 SEM image of the nano-silicon / graphene co-reinforced zinc-based bone implant prepared in Example 2 of the present invention. Detailed implementation manners

[0019] To enable those skilled in the art to better understand the technical solutions in the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0020] Example 1:

[0021] 800 mg of graphene oxide was added to 1200 mL of distilled water and ultrasonically dispersed for 3 h to form a stable graphene oxide suspension. 500 mg of silicon nanopowder (average particle size of 100 nm) was added to 50 mL of anhydrous ethanol solution and ultrasonically dispersed for 1 h. Subsequently, 0.5 mL of aminopropyltrimethoxysilane was added to the above solution, and after magnetic stirring at 40 °C for 12 h, the graphene oxide suspension was slowly added to the above silicon suspension at a volume ratio of 12:1. After magnetic stirring for 24 h, the graphene oxide-nanosilicon composite powder was obtained by centrifugation and vacuum drying. Finally, in a tubular furnace under an argon atmosphere, it was heated to 650 °C and held for 2.5 h, and a graphene-silicon carbide-nanosilicon composite powder was obtained through a thermal reduction reaction. The above graphene-silicon carbide-nanosilicon composite powder and zinc powder were sequentially added to anhydrous ethanol according to a mass ratio of 3:97 and ultrasonically dispersed for 10 min. Subsequently, the mixed solution was placed in a ball milling tank for wet ball milling. After filtration and drying, a zinc / graphene-silicon carbide-nanosilicon composite powder was obtained. The ball milling speed was controlled at 350 r / min and the ball milling time was 3 h. Using the above zinc / graphene-silicon carbide-nanosilicon composite powder as a raw material, a zinc-based bone implant was prepared by a selective laser melting process under a protective atmosphere. The laser power was controlled at 85 W, the scanning rate was 150 mm / s, the spot diameter was 50 µm, and the powder layer thickness was 0.1 mm.

[0022] It was found through testing that relatively uniform silicon nanoparticles were formed on the surface of the treated graphene, as follows Figure 1 shown, and the structure of the graphene was not damaged during the laser forming process. The nano-silicon-graphene reinforcing phase was uniformly distributed in the zinc-based bone implant, as follows Figure 2 shown, and the strength of the prepared nano-silicon-graphene synergistically reinforced zinc-based bone implant was 206 MPa.

[0023] Example 2: 800 mg of graphene oxide was added to 1200 mL of distilled water and ultrasonically dispersed for 3 h to form a stable graphene oxide suspension. 500 mg of silicon nanopowder (average particle size of 100 nm) was added to 50 mL of anhydrous ethanol solution and ultrasonically dispersed for 1 h. Subsequently, 0.5 mL of aminopropyltrimethoxysilane was added to the above solution, and after magnetic stirring at 40 °C for 12 h, the graphene oxide suspension was slowly added to the above silicon suspension at a volume ratio of 14:1. After magnetic stirring for 24 h, the graphene oxide-nano silicon composite powder was obtained by centrifugation and vacuum drying. Finally, in an argon atmosphere in a tube furnace, it was heated to 650 °C and held for 2.5 h, and a graphene-silicon carbide-nano silicon composite powder was obtained through a thermal reduction reaction. The above graphene-silicon carbide-nano silicon composite powder and zinc powder were successively added to anhydrous ethanol according to a mass ratio of 3:97 and ultrasonically dispersed for 10 min. Subsequently, the mixed solution was placed in a ball milling tank for wet ball milling. After filtration and drying, a zinc / graphene-silicon carbide-nano silicon composite powder was obtained, controlling the ball milling speed at 350 r / min and the ball milling time at 3 h; using the above zinc / graphene-silicon carbide-nano silicon composite powder as the raw material, under a protective atmosphere, a zinc-based bone implant was prepared by a selective laser melting process; controlling the laser power at 85 W, the scanning rate at 150 mm / s, the spot diameter at 50 µm, and the powder spreading thickness at 0.1 mm.

[0024] Tests found that relatively uniform silicon nanoparticles were formed on the surface of the treated graphene, as follows Figure 3 shown, and the structure of the graphene was not damaged during the laser forming process. The nano silicon-graphene reinforcing phase was uniformly distributed in the zinc-based bone implant, as follows Figure 4 shown, and the strength of the prepared nano silicon-graphene synergistically reinforced zinc-based bone implant was 195 MPa.

[0025] Example 3: 800 mg of graphene oxide was added to 1200 mL of distilled water and ultrasonically dispersed for 3 h to form a stable graphene oxide suspension. 500 mg of silicon nanopowder (average particle size of 100 nm) was added to 50 mL of anhydrous ethanol solution and ultrasonically dispersed for 1 h. Subsequently, 0.5 mL of aminopropyltrimethoxysilane was added to the above solution, and after magnetic stirring at 40 °C for 12 h, the graphene oxide suspension was slowly added to the above silicon suspension at a volume ratio of 12:1. After magnetic stirring for 24 h, the graphene oxide-nano silicon composite powder was obtained by centrifugation and vacuum drying. Finally, in an argon atmosphere in a tube furnace, it was heated to 700 °C and held for 3 h, and a graphene-silicon carbide-nano silicon composite powder was obtained through a thermal reduction reaction. The above graphene-silicon carbide-nano silicon composite powder and zinc powder were successively added to anhydrous ethanol according to a mass ratio of 3:97 and ultrasonically dispersed for 10 min. Subsequently, the mixture was placed in a ball milling jar for wet ball milling. After filtration and drying, a zinc / graphene-silicon carbide-nano silicon composite powder was obtained. The ball milling speed was controlled at 350 r / min and the ball milling time was 3 h. Using the above zinc / graphene-silicon carbide-nano silicon composite powder as a raw material, a zinc-based bone implant was prepared by a selective laser melting process under a protective atmosphere. The laser power was controlled at 85 W, the scanning rate was 150 mm / s, the spot diameter was 50 µm, and the powder spreading thickness was 0.1 mm.

[0026] Tests found that relatively uniform silicon nanoparticles were formed on the surface of the treated graphene, and the structure of graphene was not damaged during the laser forming process. The nano silicon-graphene reinforcement phase was uniformly distributed in the zinc-based bone implant, and the strength of the prepared nano silicon-graphene synergistically reinforced zinc-based bone implant was 190 MPa.

[0027] Example 4: 800 mg of graphene oxide was added to 1200 mL of distilled water and ultrasonically dispersed for 3 h to form a stable graphene oxide suspension. 500 mg of silicon nanopowder (average particle size of 100 nm) was added to 50 mL of anhydrous ethanol solution and ultrasonically dispersed for 1 h. Subsequently, 0.5 mL of aminopropyltrimethoxysilane was added to the above solution, and after magnetic stirring at 40 °C for 12 h, the graphene oxide suspension was slowly added to the above silicon suspension at a volume ratio of 12:1. After magnetic stirring for 24 h, the graphene oxide-nanosilicon composite powder was obtained by centrifugation and vacuum drying. Finally, in an argon atmosphere in a tube furnace, it was heated to 650 °C and held for 2.5 h, and the graphene-silicon carbide-nanosilicon composite powder was obtained through a thermal reduction reaction. The above graphene-silicon carbide-nanosilicon composite powder and zinc powder were successively added to anhydrous ethanol according to a mass ratio of 3:97 and ultrasonically dispersed for 10 min. Subsequently, the mixture was placed in a ball milling tank for wet ball milling. After filtration and drying, a zinc / graphene-silicon carbide-nanosilicon composite powder was obtained. The ball milling speed was controlled at 400 r / min and the ball milling time was 3 h. Using the above zinc / graphene-silicon carbide-nanosilicon composite powder as raw material, a zinc-based bone implant was prepared by a selective laser melting process under a protective atmosphere. The laser power was controlled at 85 W, the scanning rate was 150 mm / s, the spot diameter was 50 µm, and the powder spreading thickness was 0.1 mm.

[0028] The test found that relatively uniform silicon nanoparticles were formed on the surface of the treated graphene, and the structure of graphene was not damaged during the laser forming process. The nano-silicon-graphene reinforcement phase was uniformly distributed in the zinc-based bone implant, and the strength of the prepared nano-silicon-graphene synergistically reinforced zinc-based bone implant was 186 MPa.

[0029] Example 5: 800 mg of graphene oxide was added to 1200 mL of distilled water and ultrasonically dispersed for 3 h to form a stable graphene oxide suspension. 500 mg of silicon nanopowder (average particle size of 100 nm) was added to 50 mL of anhydrous ethanol solution and ultrasonically dispersed for 1 h. Subsequently, 0.5 mL of aminopropyltrimethoxysilane was added to the above solution, and after magnetic stirring at 40 °C for 12 h, the graphene oxide suspension was slowly added to the above silicon suspension at a volume ratio of 12:1. After magnetic stirring for 24 h, the graphene oxide-nano silicon composite powder was obtained by centrifugation and vacuum drying. Finally, in an argon atmosphere in a tube furnace, it was heated to 650 °C and held for 2.5 h, and a graphene-silicon carbide-nano silicon composite powder was obtained through a thermal reduction reaction. The above graphene-silicon carbide-nano silicon composite powder and zinc powder were successively added to anhydrous ethanol according to a mass ratio of 3:97 and ultrasonically dispersed for 10 min. Subsequently, the mixture was placed in a ball milling tank for wet ball milling. After filtration and drying, a zinc / graphene-silicon carbide-nano silicon composite powder was obtained, controlling the ball milling speed at 350 r / min and the ball milling time at 3 h; using the above zinc / graphene-silicon carbide-nano silicon composite powder as the raw material, in a protective atmosphere, a zinc-based bone implant was prepared by a selective laser melting process; controlling the laser power at 90 W, the scanning rate at 120 mm / s, the spot diameter at 50 µm, and the powder spreading thickness at 0.1 mm.

[0030] Tests found that relatively uniform silicon nanoparticles were formed on the surface of the treated graphene, and the structure of graphene was not damaged during the laser forming process. The nano silicon-graphene reinforcing phase was uniformly distributed in the zinc-based bone implant, and the strength of the prepared nano silicon-graphene synergistically reinforced zinc-based bone implant was 180 MPa.

[0031] Comparative Example 1: Other conditions of this comparative example were the same as those of Example 1, except that in this comparative example, the graphene oxide suspension and the silicon suspension were slowly added to it at a volume ratio of 15:1. Tests found that fewer silicon nanoparticles were generated on the surface of the treated graphene powder, and graphene was partially agglomerated in the zinc matrix after selective laser melting. The strength of the prepared nano silicon-graphene synergistically reinforced zinc-based bone implant was 148 MPa.

[0032] Comparative Example 2: Other conditions of this comparative example were the same as those of Example 1, except that in this comparative example, the graphene oxide-nano silicon composite powder was heated to 500 °C and held for 2.5 h in an argon atmosphere in a tube furnace. Tests found that no in-situ reaction occurred between graphene and silicon nanoparticles to form silicon carbide, and graphene oxide was not completely reduced to graphene. The strength of the prepared nano silicon-graphene synergistically reinforced zinc-based bone implant was 123 MPa.

[0033] Comparative Example 3: Other conditions of this comparative example are the same as those of Example 1, except that the ball milling speed in this comparative example is 500 r / min and the ball milling time is 3 h. Tests found that after ball milling, part of the graphene powder was cut and deformed, the sheet diameters were different, and part of the silicon nanoparticles generated on the surface peeled off. The strength of the prepared nano-silicon / graphene synergistically enhanced zinc-based bone implant was 125 MPa.

[0034] Comparative Example 4: Other conditions of this comparative example are the same as those of Example 1, except that the laser power is controlled at 150 W and the scanning rate is 100 mm / s in this comparative example. Tests found that during the laser forming process, the zinc powder was severely balled and part of the graphene structure was damaged. The strength of the prepared nano-silicon / graphene synergistically enhanced zinc-based bone implant was 94 MPa.

[0035] As can be seen from the above, the performances of the products obtained in Comparative Examples 1 - 4 are much worse than those of the products obtained in Examples 1 - 5.

[0036] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A preparation method of a nano-silicon / graphene synergistically enhanced zinc-based bone implant, characterized in that, It includes the following operation steps: S1. Add a certain amount of graphene oxide into distilled water, and ultrasonically disperse it for a period of time to form a stable graphene oxide suspension; S2. Take a certain amount of silicon nano-powder and pour it into an anhydrous ethanol solution to form a silicon alcohol solution. After ultrasonically dispersing it for a period of time, add a certain amount of 3-aminopropyltrimethoxysilane into the above silicon alcohol solution and stir to form a silicon suspension; S3. Slowly add the graphene oxide suspension prepared in step S1 to the silicon suspension prepared in step S2 at a certain ratio, stir evenly to form a mixed solution. The mixed solution is successively centrifuged and vacuum dried to obtain graphene oxide-nano silicon mixed powder. The graphene oxide-nano silicon mixed powder is then subjected to a thermal reduction reaction to obtain a graphene-silicon carbide-nano silicon composite powder; S4. Place the graphene-silicon carbide-nano silicon composite powder and zinc powder prepared in step S3 in an anhydrous ethanol solution in a certain mass ratio in sequence and ultrasonically disperse them. Then wet ball-mill the dispersed mixed solution, and after filtration and drying, obtain a zinc / graphene-silicon carbide-nano silicon mixed powder; S5. Using the zinc / graphene-silicon carbide-nano silicon mixed powder prepared in step S4 as a raw material, under a protective atmosphere, a zinc-based bone implant is prepared by a selective laser melting process.

2. The preparation method of the nano-silicon / graphene synergistically enhanced zinc-based bone implant according to claim 1, characterized in that, The average particle size of the silicon nano-powder in step S2 is 50 - 200 nm.

3. The preparation method of the nano-silicon / graphene synergistically enhanced zinc-based bone implant according to claim 1, characterized in that In step S3, the volume ratio of the graphene oxide suspension to the silicon suspension is 10:1 - 14:

1.

4. The preparation method of the nano-silicon / graphene synergistically reinforced zinc-based bone implant according to claim 1, characterized in that, In step S3, the graphene oxide-nano silicon mixed powder is heated to 600 - 800 °C and kept warm for 2 - 3 h in an argon atmosphere in a tubular furnace for a thermal reduction reaction.

5. The preparation method of the nano-silicon / graphene synergistically reinforced zinc-based bone implant according to any one of claims 1-4, characterized in that, In step S4, the mass ratio of the graphene-silicon carbide-nano silicon composite powder to the zinc powder is 2:98 - 5:

95.

6. The preparation method of the nano-silicon / graphene synergistically reinforced zinc-based bone implant according to any one of claims 1-4, characterized in that, In step S4, the ball-milling speed is 250 - 400 r / min, and the ball-milling time is 2 - 4 h.

7. The preparation method of the nano-silicon / graphene synergistically reinforced zinc-based bone implant according to any one of claims 1-4, characterized in that, In step S5, the power of the laser is 80 - 100 W, the scanning rate of the laser is 100 - 200 mm / s, the spot diameter of the laser is 45 - 55 µm, and the powder layer thickness is 0.1 - 0.2 mm.

8. A nano-silicon / graphene synergistically enhanced zinc-based bone implant, characterized in that, It is prepared by using the preparation method of the nano-silicon-graphene synergistically enhanced zinc-based bone implant according to any one of claims 1 - 7 above.

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