TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy and preparation method thereof

Abstract

The application discloses a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy and a preparation method thereof, relates to the technical field of medium-entropy alloys, and comprises a chemical formula Ti x Zr y Nb z M h , M is Cu or Sr, x, y, z and h are respectively the mole percentages of chemical elements Ti, Zr, Nb and M, 0 < x = y = z <= 35, 3 < h <= 10, the antibacterial rate reaches 50% to 60% when M is Cu, high strength and heat shock resistance are achieved, the antibacterial rate reaches 30% to 50% when M is Sr, high strength and heat shock resistance are achieved, the TiZrNbCu or TiZrNbSr alloy shows excellent heat shock resistance after 500 DEG C electric pulse annealing, and material cracks and failures caused by thermal stress can be effectively reduced. The excellent heat shock resistance is due to the unique microstructure and excellent thermal stability of the alloy, and the TiZrNbCu or TiZrNbSr alloy can be widely applied to fields with high requirements on heat shock resistance under high-temperature environments.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high-entropy alloys, and particularly relates to a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy and a preparation method thereof. BACKGROUND

[0002] Medium-entropy alloys are between traditional alloys and high-entropy alloys, inheriting the excellent performance of high-entropy alloys, and at the same time, due to the smaller number of main elements, the mixing entropy is close to that of traditional alloys, and better industrial application potential is achieved. However, the application of traditional alloys under extreme conditions, especially in high-temperature environments, still faces many challenges, such as cracking tendency under thermal shock or difficulty in balancing strength and toughness, and poor processing adaptability.

[0003] TiZrNb alloys have become a research hotspot due to their light weight or high strength and excellent high-temperature resistance. Ti, Zr and Nb are all elements with high melting points and good oxidation resistance, and the alloys composed of them exhibit significant stability in high-temperature environments. However, although Ti-Zr-Nb exhibits good performance in high-temperature fields, its thermal shock resistance and comprehensive mechanical properties still have room for improvement. Especially under rapid temperature rise and fall conditions, thermal stress concentration can easily lead to the generation and expansion of material microcracks, thereby reducing the service life. In order to solve these problems, researchers propose to dope alloy elements in the Ti-Zr-Nb system to further optimize the material performance. The TiZrNb medium-entropy alloy itself does not have the characteristics of sterilization and disinfection, which may cause potential infection risks in biomedical applications.

[0004] At present, the research on this system of alloys is mainly concentrated in the laboratory stage, and the industrialized preparation, process optimization and long-term service performance stability are still technical bottlenecks to be broken through. The present application proposes a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy and a preparation method thereof in view of the problems in the above technical background. By reasonably designing the alloy composition and heat treatment process, the present application realizes the synergistic optimization of the strength, antibacterial property, toughness and thermal shock resistance of the material in a low-density system, providing a new research idea and technical approach for the practical application of medium-entropy alloys. SUMMARY

[0005] The present application aims to provide a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy and a preparation method thereof to solve the problems raised in the above background.

[0006] To solve the above technical problems, the present application is realized by the following technical scheme:

[0007] The present application is a preparation method of a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy, including a chemical formula represented as Ti xZr y Nb z M h , M is Cu or Sr, x, y, z, h are respectively the mole percentage of chemical elements Ti, Zr, Nb, M, 0 < x = y = z < 35, 3 < h < 10, when M is Cu, the antibacterial rate reaches 50%-60%, with high strength and heat shock resistance, when M is Sr, the antibacterial rate reaches 30%-50%, with high strength and heat shock resistance, the manufacturing steps are as follows: step 1, taking intermediate alloy TiZr, TiNb and TiM as raw materials, using a medium frequency induction furnace to smelt;

[0008] Step 2, the middle entropy alloy ingot is cut into a sheet by wire cutting;

[0009] Step 3, the sheet is put into a box muffle furnace for solid solution treatment, and then is put into water for water quenching after the solid solution treatment is completed;

[0010] Step 4, the middle entropy alloy material prepared in step 3 is taken out and annealed under the condition of electric pulse, and then is cooled, finally the implantable middle entropy alloy material with high strength, excellent antibacterial performance and heat shock resistance is obtained.

[0011] Further, the equal mole ratio of Ti, Zr, Nb in the alloy is calculated according to M, and the mole percentage of M is 3% < h < 10%, the mole percentage of Ti, Zr, Nb is calculated by calculation Then the content of three intermediate alloys TiZr, TiNb, TiM is calculated according to the following equation: f TiZr ·TiZr Ti +f TiNb ·TiNb Ti +f TiM ·TiM Ti =x; f TiZr ·TiZr Zr =x; f TiNb ·TiNb Nb =x; f TiM ·TiM M =h; f TiZr +f TiNb +f TiM =1; f TiZr , f TiNb , f TiM are respectively the mass percentage required in the smelting process of TiZr, TiNb, TiM intermediate alloy; TiZr Ti , TiZr Zr , TiNb Ti , TiNb Nb , TiM M、 TiM Ti are the component percentage of each intermediate alloy.

[0012] Further, the power of the intermediate frequency induction furnace is 50-100 kW, the induction furnace needs to be preheated to 500-600 DEG C during the smelting process, then gradually heated in the empty state, the heating rate is 10 DEG C / min, heated to 1400 DEG C, the three raw materials TiZr, TiM and TiNb are gradually put into the intermediate frequency induction furnace, the frequency of the intermediate frequency induction furnace is set between 500 Hz and 5 kHz, the baffle is used at the furnace mouth, the baffle is used for heat insulation, anti-oxidation, anti-pollution and safety protection, ensures that the smelting process is carried out smoothly and improves the quality of the final alloy, after the smelting is completed, the alloy liquid is poured into the preheated mold, the mold temperature is kept between 300-500 DEG C, after the alloy liquid in the mold is cooled to room temperature, the final TiZrNbM entropy alloy is obtained.

[0013] Further, the thickness of the thin slice cut by the center line is 2 mm.

[0014] Further, the solid solution treatment temperature is 1000 DEG C, and the solid solution treatment time is 1 h.

[0015] Further, the electric pulse heating frequency is 1-10 kHz, and the pulse width is 10-500 microseconds, which ensures that the alloy temperature is uniformly raised and overheating is avoided.

[0016] Further, the pulse current intensity is 30-100 A, which ensures sufficient heating effect without damaging the alloy.

[0017] Further, the annealing process is kept for 1 hour, and the uniform heating of the alloy promotes the homogenization of the grain and the stress release.

[0018] Further, the entropy alloy prepared by the TiZrNb-based Cu or Sr doped antibacterial implantable entropy alloy preparation method.

[0019] The present application has the following beneficial effects:

[0020] 1、TiZrNbCu alloy after 500 DEG C electric pulse annealing shows excellent thermal shock resistance, which can effectively reduce the material cracks and failures caused by thermal stress. Its excellent thermal shock resistance is due to the unique microstructure and excellent thermal stability of the alloy, which can be widely used in high temperature environment and has high requirements for thermal shock resistance.

[0021] 2、TiZrNb-based Cu doped entropy alloy has significant antibacterial performance, and shows high inhibition effect on common bacteria such as Staphylococcus aureus. This performance is due to the uniform distribution and continuous release of antibacterial ions of Cu, combined with the biocompatibility of the alloy, so that it becomes an ideal material for implantable medical devices, effectively reduces the risk of infection and improves the safety and reliability of the implant.

[0022] 3、TiZrNbSr alloy after 500℃ electric pulse annealing, shows excellent thermal shock resistance, effectively reduces the cracks and failure caused by thermal stress. Enhances the thermal stability and thermal fatigue resistance. The alloy exhibits strong oxidation resistance and good thermal expansion matching at high temperature, suitable for high temperature environment with high requirements for thermal shock resistance.

[0023] 4、TiZrNb base Sr doped middle entropy alloy has significant antibacterial performance, can effectively inhibit the growth of common bacteria such as staphylococcus aureus and escherichia coli. The incorporation of Sr element improves the surface properties of the alloy, which may inhibit the adhesion and reproduction of bacteria by releasing antibacterial ions. Combined with the corrosion resistance of TiZrNb alloy itself, these alloys have wide application potential in medical devices, environmental protection and other fields.

[0024] Of course, the implementation of any product of the present application does not necessarily require all the advantages described above. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0026] Figure 1-1 XRD pattern of TiZrNbCu alloy, TiZrNbSr alloy and TiZrNb alloy in annealed state.

[0027] Figure 1-2 XRD pattern of TiZrNbSr alloy in annealed state.

[0028] Figure 2 TiZrNb alloy sample graph.

[0029] Figure 3 TiZrNb alloy 500℃ annealed sample graph.

[0030] Figure 4-1 TiZrNbCu alloy 500℃ annealed sample graph.

[0031] Figure 4-2 TiZrNbSr alloy 500℃ annealed sample graph.

[0032] Figure 5 TiZrNbCu alloy, TiZrNbSr alloy and TiZrNb alloy 500℃ hardness graph.

[0033] Figure 6Hardness map of TiZrNbCu alloy, TiZrNbSr alloy and TiZrNb alloy at different rolling rates.

[0034] Figure 7 Stress-strain map of TiZrNbCu alloy, TiZrNbSr alloy and TiZrNb alloy at 70% rolling rate.

[0035] Figure 8-1 Metallographic map of TiZrNbCu alloy in 500℃ annealing state.

[0036] Figure 8-2 Metallographic map of TiZrNbSr alloy in 500℃ annealing state. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be apparently and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those of ordinary skill in the art without any creative work fall within the protection scope of the present application.

[0038] Please refer to Figures 1-1 to 8-2 The present application is a TiZrNb-based Cu or Sr doped antibacterial implantable medium-entropy alloy and a preparation method thereof, which comprises a chemical formula Ti x Zr y Nb z M h , M is Cu or Sr, x, y, z, h are respectively the mole percentages of chemical elements Ti, Zr, Nb and M, 0

[0039] Step 1: using intermediate alloy TiZr, TiNb and TiM as raw materials, using a medium-frequency induction furnace to smelt;

[0040] Step 2: medium-entropy alloy ingot is cut into thin slices by wire cutting;

[0041] Step 3: the thin slices are put into a box muffle furnace for solid solution treatment, and then are put into water for water quenching after the solid solution treatment is completed;

[0042] Step 4, the step 3 prepared entropy alloy material is taken to carry out annealing treatment under electric pulse condition, and then cooling, finally the implantable medium entropy alloy material with high strength, excellent antibacterial performance and heat shock resistance is obtained. The Cu or Sr doped TiZrNb medium entropy alloy exhibits alloy composition, realizes high uniformity, and avoids composition segregation. The solid solution treatment combined with electric pulse annealing makes the material have high strength, exhibits good thermal stability in high temperature environment, and the thermal stress resistance is significantly improved.

[0043] The equimolar ratio of Ti, Zr and Nb in the alloy according to M is calculated, and the mole percentage of M is 3% < h < 10%, the mole percentage of Ti, Zr and Nb is calculated Then the content of TiZr, TiNb and TiM intermediate alloy is calculated according to the following equation: f TiZr ·TiZr Ti +f TiNb ·TiNb Ti +f TiM ·TiM Ti =x;f TiZr ·TiZr Zr =x;f TiNb ·TiNb Nb =x;f TiM ·TiM M =h;f TiZr +f TiNb +f TiM =1;f TiZr , f TiNb , f TiM The mass percentage required in the smelting process of TiZr, TiNb and TiM intermediate alloy respectively; TiZr Ti , TiZr Zr , TiNb Ti , TiNb Nb , TiM M、 TiM Ti The composition percentage of each intermediate alloy.

[0044] The power of the intermediate frequency induction furnace is 50-100 kW, the induction furnace needs to be preheated to 500-600 ℃ during the smelting process, then gradually heated in the empty state, the heating rate is 10 ℃ / min, heated to 1400 ℃, the three raw materials TiZr, TiM and TiNb are gradually put into the intermediate frequency induction furnace, the frequency of the intermediate frequency induction furnace is set between 500 Hz and 5 kHz, a baffle is used at the furnace mouth, the baffle is used for heat insulation, anti-oxidation, anti-pollution and safety protection, to ensure the smooth progress of the smelting process and improve the quality of the final alloy, after the smelting is completed, the alloy liquid is poured into a preheated mold, the temperature of the mold is kept between 300-500 ℃, after the alloy liquid in the mold is cooled to room temperature, the final TiZrNbM entropy alloy is obtained.

[0045] The thickness of the thin slice cut by the wire is 2 mm.

[0046] The solid solution treatment temperature is 1000 ℃, and the solid solution treatment time is 1 h.

[0047] The frequency of the electric pulse heating is 1-10 kHz, and the pulse width is 10-500 microseconds, which ensures uniform temperature rise of the alloy and avoids overheating.

[0048] The intensity of the pulse current is 30-100 A, which ensures sufficient heating effect without damaging the alloy.

[0049] The annealing process is kept for 1 hour, and the uniform heating of the alloy promotes the homogenization of the grains and the stress release.

[0050] The TiZrNb-based Cu-doped antibacterial implantable entropy alloy prepared by the above method.

[0051] Example 1

[0052] A TiZrNb-based Cu-doped antibacterial implantable entropy alloy, a TiZrCu alloy is prepared, and when the Cu content is 3%, 6%, 8% or 10%:

[0053] (1) Put high-purity TiZr, TiNb and TiCu as raw materials into the intermediate frequency induction furnace, and melt them by induction heating. After the smelting is completed, the alloy liquid is poured into a preheated mold, the temperature of the mold is generally kept between 300-500 ℃, and the alloy liquid in the mold is cooled to room temperature after the alloy liquid in the mold is cooled to room temperature, the final TiZrNbCu entropy alloy is obtained.

[0054] (2) The above alloy ingot is cut into a thin slice with a thickness of 2 mm by wire cutting;

[0055] (3) Put the thin slice into a box-type muffle furnace for solid solution treatment, the solid solution temperature is 1000 ℃, and the holding time is 1 hour, and immediately water quenching after solid solution;

[0056] (4) Annealing temperature under electric pulse condition is 500℃, time is 1 hour.

[0057] The TiZrNbCu alloy prepared in Example 1 is analyzed by XRD, and the results are shown in Figure 1-1 Figure 3 Figure 4-1 The hardness of the annealed state and different rolling rates is shown in Figure 5 Figure 6 The stress-strain curve obtained by the tensile testing machine is shown in Figure 7 The metallographic image of the TiZrNbCu alloy annealed at 500℃ is shown in Figure 8-1

[0058] Figure 1-1 The peak of TiZrNbCu in the middle of TiZrNb has changed significantly, especially in the range of 40° to 50°, indicating that the crystal structure has changed significantly after adding Cu. The introduction of Cu promotes the formation of TiCu3 phase. The diffraction peak of TiZrNbCu is more sharp, indicating that it has higher crystallinity or more stable crystal structure, which helps to improve the performance of the material such as mechanical strength. Figure 2 The surface of the TiZrNb alloy wire cutting sample has no cracks before heat treatment. After annealing at 500℃, the surface of TiZrNb alloy has obvious cracks as shown in Figure 3 , and no obvious cracks after adding Cu as shown in Figure 3 and Figure 4-1 The hardness of TiZrNb and TiZrNbCu alloys is shown in Figure 5 and Figure 6 The addition of Cu significantly improves the hardness, which is attributed to the solid solution strengthening effect and the fine grain structure formed during processing, at the same time, the higher cold rolling rate leads to the increase of dislocation density, which further enhances the hardness and strength of the material. The stress-strain curve is shown in Figure 7 The addition of Cu significantly improves the tensile strength and ductility of the alloy, at the same time, the plastic deformation ability of TiZrNbCu is stronger, these results show that the addition of Cu effectively enhances the strength and ductility of the alloy through solid solution strengthening and microstructure refinement effect.

[0059] In the present application, other alloy compositions are prepared by the same method as in Example 1, see Table 1 below:

[0060] Table 1

[0061] Element Ti Zr Nb Cu Ingredient One 32.3 32.3 32.3 3 Ingredient Two 31.3 31.3 31.3 6 Ingredient Three 30.7 30.7 30.7 8 Ingredient Four 30 30 30 10

[0062] ​​​​The TiZrNbCu alloy of the present application exhibits excellent thermal shock resistance after 500℃ electric pulse annealing, which can effectively reduce material cracks and failures caused by thermal stress. The excellent thermal shock resistance is due to the unique microstructure and excellent thermal stability of the alloy, which can be widely used in high-temperature environments with high requirements for thermal shock resistance.

[0063] The TiZrNb-based Cu-doped entropy alloy of the present application has significant antibacterial performance and exhibits high inhibition effect on common bacteria such as Staphylococcus aureus. This performance is due to the uniform distribution and sustained release of antibacterial ions of Cu, combined with the biocompatibility of the alloy, making it an ideal material for implantable medical devices, effectively reducing the risk of infection and improving the safety and reliability of implants.

[0064] The Cu element of the present application has excellent thermal conductivity and oxidation resistance. High thermal conductivity can significantly improve the heat conduction capacity of the alloy, thereby effectively relieving the temperature gradient and thermal stress concentration caused by it under thermal shock conditions. And Cu can refine the grains in the alloy, optimize the microstructure, and improve the strength and toughness matching of the alloy. At the same time, it helps to improve the plasticity of the alloy, making it show better adaptability in the processing process. The introduction of Cu element not only can significantly improve the mechanical properties of TiZrNb entropy alloy, but also can effectively inhibit the growth and reproduction of bacteria due to its good antibacterial properties. The addition of Cu can form an antibacterial environment on the surface of the implant by releasing copper ions, thereby reducing the risk of infection and improving the safety of the implant. The introduction of Cu can also improve the processability and wear resistance of the alloy, making TiZrNb entropy alloy more advantageous in manufacturing and use.

[0065] Example 2

[0066] TiZrNb-based Sr-doped antibacterial implantable entropy alloy, prepare TiZrNbSr alloy, when the content of Sr is 3%, 6%, 8% or 10%;

[0067] (1) The TiZrNbSr alloy ingot after medium-frequency induction furnace melting is subjected to wire cutting to obtain a sheet with a thickness of 2mm;

[0068] (2) The sheet is placed in a box-type muffle furnace for solid solution treatment, the solid solution temperature is 1000℃, and the holding time is 1 hour. After solid solution treatment, water quenching is immediately performed;

[0069] (3) The annealing temperature under electric pulse conditions is 500℃, and the time is 1 hour.

[0070] The TiZrNbSr alloy prepared in Example 2 is subjected to XRD analysis, and the results are shown in Figure 1-2 After 500℃ annealing, the samples of TiZrNb and TiZrNbSr alloys are as shown in Figure 3 andFigure 4-2 The hardness of the annealed state and different rolling rates is shown in Figure 5 and Figure 6 The stress-strain curve obtained by the tensile testing machine is shown in Figure 7 The metallographic diagram of TiZrNbSr alloy in the annealed state at 500℃ is shown in Figure 8-2 .

[0071] Figure 1-2 The diffraction characteristic peaks of the typical body-centered cubic (BCC) structure crystal surface are (110), (200), and (211), and the (110) crystal surface is the main orientation. The distribution of such peaks indicates that the TiZrNbSr alloy may have a single BCC structure, and the introduction of Sr helps to stabilize the BCC structure. After annealing at 500℃, the TiZrNb alloy surface is obviously cracked as shown in Figure 3 , and after adding Sr, there is no obvious crack as shown in Figure 3 and Figure 4-2 The hardness of TiZrNb and TiZrNbSr alloys is shown in Figure 5 and Figure 6 The hardness of TiZrNbSr alloy in the annealed and different rolling rate states is obviously higher than that of TiZrNb alloy, and the addition of Sr improves the tensile strength and ductility of the alloy, and the plastic deformation ability of TiZrNbSr is stronger as shown in Figure 7 .

[0072] In the present application, other alloy compositions are prepared by the same method as in Example 2, as shown in Table 2 below:

[0073] Table 2

[0074]

[0075]

[0076] The TiZrNbSr alloy of the present application after 500℃ electric pulse annealing shows excellent thermal shock resistance, effectively reducing the cracks and failure caused by thermal stress. The thermal stability and thermal fatigue resistance are enhanced. The alloy exhibits strong oxidation resistance and good thermal expansion matching at high temperature, and is suitable for application fields with high requirements for thermal shock resistance in high temperature environment.

[0077] The TiZrNb-based Sr-doped entropy alloy of the present application has significant antibacterial performance, which can effectively inhibit the growth of common bacteria such as Staphylococcus aureus and Escherichia coli. The incorporation of Sr element improves the surface properties of the alloy, which may inhibit bacterial adhesion and reproduction by releasing antibacterial ions. Combined with the corrosion resistance of TiZrNb alloy itself, these alloys have wide application potential in the fields of medical devices and environmental protection.

[0078] In the description of the application, references to "one embodiment", "an example", "certain examples" etc. mean that a particular feature, structure, material or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. The appearances of the phrases "in one embodiment", "an example", "certain examples" etc. in various places in the specification are not necessarily referring to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments or examples.

[0079] The preferred embodiments of the application disclosed above are only to help explain the application. The preferred embodiments do not describe all of the details of the application and limit the application to the specific embodiments described. Obviously, many modifications and variations of the application can be made in light of the teachings above. The embodiments are chosen and described in order to best explain the principles of the application and its practical application and to enable others skilled in the art to best utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy, characterized in that: The chemical formula of the medium entropy alloy is Ti x Zr y Nb z M h , M is Cu or Sr, x, y, z, h are the molar percentages of chemical elements Ti, Zr, Nb, and M respectively, 30≤x=y=z<32.3, 3<h≤10, x+y+z+h =100, when M is Cu, the antibacterial rate reaches 50%-60%, with high strength and heat shock resistance, when M is Sr, the antibacterial rate reaches 30%-50%, with high strength and heat shock resistance, and the production steps are as follows: Step 1: Using master alloys TiZr, TiNb and TiM as raw materials, smelting them in a medium frequency induction furnace; Step 2: obtaining thin slices from the medium entropy alloy ingot by wire cutting; Step 3: The slice is placed in a box-type muffle furnace for solution treatment, and after the solution treatment is completed, it is placed in water for water quenching. The solution treatment temperature is 1000° C. and the solution treatment time is 1 hour. Step 4: The medium-entropy alloy material obtained in step 3 is annealed under electric pulse conditions and then cooled to obtain an implantable medium-entropy alloy material with high strength, excellent antibacterial properties and thermal shock resistance. The annealing temperature under the electric pulse conditions is 500°C and the annealing time is 1 hour.

2. The method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to claim 1, characterized in that: The molar ratio of Ti, Zr and Nb in the alloy is calculated based on M, and the molar percentage of M is 3%< ≤ 10%, the molar percentages of Ti, Zr, and Nb are calculated as follows: %, and then calculate the contents of TiZr, TiNb and TiM master alloys according to the following equation: TiZr TiZr Ti +f TiNb TiNb Ti + f TiM ·TiM Ti =x;f TiZr TiZr Zr = y; f TiNb TiNb Nb = z;f TiM ·TiM M =h;f TiZr + f TiNb + f TiM =1;f TiZr 、f TiNb 、f TiM are the mass percentages of TiZr, TiNb and TiM master alloys required in the smelting process; TiZr Ti 、TiZr Zr 、TiNb Ti 、TiNb Nb 、TiM M、 TiM Ti is the percentage of the components of each master alloy.

3. The method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to claim 1, characterized in that: The power of the medium frequency induction furnace is 50-100 kW. During the smelting process, the induction furnace needs to be preheated to 500-600°C, and then gradually heated in an unloaded state at a heating rate of 10°C / min to 1400°C. The three raw materials of TiZr, TiM and TiNb are gradually added to the medium frequency induction furnace. The frequency of the medium frequency induction furnace is set between 500 Hz and 5 kHz. A baffle is used at the furnace mouth for heat insulation, oxidation protection, pollution prevention and safety protection, ensuring a smooth smelting process and improving the quality of the final alloy. After the smelting is completed, the alloy liquid is poured into a preheated mold, and the mold temperature is maintained between 300-500°C. After the alloy liquid in the mold is cooled to room temperature, the final TiZrNbM medium-entropy alloy is obtained.

4. The method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to claim 1, characterized in that: The thickness of the wire-cut slices is 2 mm.

5. The method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to claim 1, characterized in that: The electric pulse heating frequency is 1-10 kHz and the pulse width is 10-500 microseconds, which ensures that the alloy temperature rises evenly and avoids overheating.

6. The method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to claim 1, characterized in that: The pulse current intensity is 30-100 A, ensuring sufficient heating effect without damaging the alloy.

7. A TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy, prepared by the method for preparing a TiZrNb-based Cu or Sr-doped antibacterial implantable medium-entropy alloy according to any one of claims 1 to 6.

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