Biomedical antibacterial high-entropy alloy TiZrHfNbCu and preparation method thereof
By preparing TiZrHfNbCu high entropy alloy, the problems of high Young's modulus and cytotoxic elements of existing biomedical metal materials were solved, and medical high entropy alloys with low Young's modulus, excellent antibacterial properties and good biocompatibility were achieved, with excellent antibacterial properties and stable mechanical properties.
Patent Information
- Application Number
- CN202510340805.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-21
- Publication Date
- 2025-07-11
AI Technical Summary
Existing biomedical metal materials have problems with high Young's modulus and cytotoxic elements, which leads to the implant being prone to stress shielding effects and bacterial infection.
A high-entropy alloy composed of Ti, Zr, Hf, Nb and Cu elements was prepared by vacuum argon arc smelting method, and an appropriate amount of Cu elements was added to improve antibacterial performance while maintaining good biocompatibility and low Young's modulus.
It has achieved a medical high-entropy alloy with low Young's modulus, excellent antibacterial properties and good biocompatibility, avoiding the problem of component inhomogeneity caused by Cu elements, and has excellent antibacterial properties and stable mechanical properties.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of medical implant materials, and particularly relates to a bio-medical antibacterial TiZrHfNbCu high-entropy alloy and a preparation method thereof. Background Art
[0002] Bio-medical metallic materials are metals or alloys used as bio-medical materials, which have strong mechanical strength and fatigue resistance and are widely used as load-bearing implant materials. The three most commonly used clinically at present are mainly divided into the following three types: titanium and titanium alloys, cobalt alloys, and stainless steels. However, they all face the following problems in clinical applications: First, the elastic modulus is quite different from that of human bones, which is likely to cause the "stress shielding effect" and induce the weakening of normal tissues around the implant; second, all three alloys contain elements with cytotoxicity or harmfulness, and are likely to release toxic metal ions in tissue fluid, which is harmful to human tissues.
[0003] High-entropy alloys are alloys with excellent properties. High-entropy alloys have four typical effects: high-entropy effect, sluggish diffusion effect, cocktail effect, and lattice distortion effect. Among them, the cocktail effect enables high-entropy alloys to have controllable properties, and the desired properties can be obtained by changing the types or contents of components in the high-entropy alloy. In the field of biomedicine, high-entropy alloys have low Young's modulus, hardness similar to that of bones, high specific strength, etc., making them have good application potential in the field of medical health.
[0004] Medical high-entropy alloys are often composed of non-cytotoxic elements such as Ti, Zr, Nb, Ta, etc. as the main components, and can obtain lower Young's modulus and better biocompatibility. However, the currently common medical high-entropy alloys all lack necessary antibacterial properties and are prone to bacterial infection after being implanted into the human body. And how to use each element in combination to obtain a medical high-entropy alloy with good cytocompatibility, low Young's modulus, and good antibacterial properties is one of the problems that people need to solve. Summary of the Invention
[0005] In view of the problems of high Young's modulus and poor cytotoxic elements existing in the existing bio-medical metallic materials, the present invention provides a bio-medical high-entropy alloy with both low Young's modulus, biocompatibility, and excellent antibacterial properties and a preparation method thereof by doping with Cu element. The method of the present invention also solves the problem of uneven melting due to the large difference in melting points between Cu and other elements.
[0006] The purpose of the present invention is achieved through the following technical solutions:
[0007] A bio-medical high-entropy alloy is composed of five elements, namely Ti, Zr, Hf, Nb, and Cu, and its composition is TiZrHfNbCu x, where 0 < x ≤ 1.2, and the molar ratio of Ti, Zr, Hf, Nb, and Cu is 1:1:1:1:x, and x is preferably 0.7 - 1.2.
[0008] The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu includes the following steps: Ti, Zr, Hf, Nb, and Cu are subjected to vacuum argon arc melting to obtain the antibacterial high-entropy alloy.
[0009] Specifically, the preparation method is to mix Ti, Zr, and Cu and conduct vacuum argon arc melting to obtain a Ti-Zr-Cu intermediate alloy; mix Hf and Nb and conduct vacuum argon arc melting to obtain an Hf-Nb intermediate alloy; mix the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy, and conduct vacuum argon arc melting to obtain the antibacterial high-entropy alloy.
[0010] During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3 Pa, and then argon is filled to 0.02 Pa, which can avoid oxidation during the alloy melting process.
[0011] The melting conditions of the Ti-Zr-Cu intermediate alloy: the arc current is 180 - 200 A, the melting time per time is 180 s; the number of flipping melting times is 5 - 6 times.
[0012] The melting conditions of the Hf-Nb intermediate alloy: the arc current is 200 - 250 A, the melting time per time is 180 s, and the number of flipping melting times is 5 - 6 times.
[0013] When the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy are mixed and subjected to vacuum argon arc melting, the conditions are:
[0014] The arc current is 200 - 250 A, the melting time per time is 180 s; the number of melting times is 8 - 10 times.
[0015] The content of each of the five raw material particles of Ti, Zr, Hf, Nb, and Cu is 99.9%.
[0016] After the melting of the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy is completed, cooling is carried out.
[0017] The cooling method is water cooling for 10 - 20 min
[0018] Compared with the prior art, the present invention has the following advantages:
[0019] 1. The medical antibacterial high-entropy alloy of the present invention has excellent antibacterial properties;
[0020] 2. When the Cu element is added to the medical antibacterial high-entropy alloy of the present invention to obtain antibacterial properties, it does not affect the good biocompatibility of the original TiZrHfNb alloy;
[0021] 3. After the Cu element is added to the medical antibacterial high-entropy alloy of the present invention, the Young's modulus of the alloy does not increase significantly. Description of the Drawings
[0022] Figure 1 X-ray diffraction results of antibacterial high-entropy alloys with different Cu contents prepared in Examples 1 to 6; Example 1: TZHN, Example 2: TZHN-Cu0.2, Example 3: TZHN-Cu0.4, Example 4: TZHN-Cu0.6, Example 5: TZHN-Cu0.8, Example 6: TZHN-Cu1.0;
[0023] Figure 2 SEM images of antibacterial high-entropy alloys with different Cu contents prepared in Examples 1 to 6;
[0024] Figure 3 Results of plate coating after co-culturing antibacterial high-entropy alloys with different Cu contents prepared in Examples 1 to 6 with Staphylococcus epidermidis for 24 h; Example 1: TZHN, Example 2: TZHN-Cu0.2, Example 3: TZHN-Cu0.4, Example 4: TZHN-Cu0.6, Example 5: TZHN-Cu0.8, Example 6: TZHN-Cu1.0;
[0025] Figure 4 Line graph of absorbance values at 450 nm after co-culturing antibacterial high-entropy alloys with different Cu contents prepared in Examples 1 to 6 with human umbilical vein endothelial cells for 24 h; Example 1: TZHN, Example 2: TZHN-Cu0.2, Example 3: TZHN-Cu0.4, Example 4: TZHN-Cu0.6, Example 5: TZHN-Cu0.8, Example 6: TZHN-Cu1.0;
[0026] Figure 5 Compression stress-strain curves of antibacterial high-entropy alloys with different Cu contents prepared in Examples 1 to 6 at room temperature; Example 1: TZHN, Example 2: TZHN-Cu0.2, Example 3: TZHN-Cu0.4, Example 4: TZHN-Cu0.6, Example 5: TZHN-Cu0.8, Example 6: TZHN-Cu1.0. Detailed Embodiments
[0027] The following further describes the TiZrHfNbCu high-entropy alloy of the present invention with reference to the embodiments, but the protection scope of the present invention is not limited to the content of the embodiments.
[0028] Example 1
[0029] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNb.
[0030] The preparation method of the TiZrHfNb high-entropy alloy is as follows:
[0031] After weighing Ti, Zr, Hf, and Nb with a purity of 99.9% according to a molar ratio of 1:1:1:1, vacuum argon arc melting is used to obtain the high-entropy alloy. Specifically: Ti and Zr are stacked together for vacuum argon arc melting to obtain a Ti-Zr intermediate alloy; Hf and Nb are stacked together and vacuum argon arc melted to obtain an Hf-Nb intermediate alloy; the Ti-Zr intermediate alloy and the Hf-Nb intermediate alloy are stacked together and vacuum argon arc melted to obtain the high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3 Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. The number of times of flipping and melting for the Ti-Zr intermediate alloy ingot during preparation is 5 - 6 times, the melting time for each time is 180 s, and the arc current for melting the intermediate alloy is 180 - 200 A. The number of times of flipping and melting for the Hf-Nb intermediate alloy ingot during preparation is 5 - 6 times, the melting time for each time is 180 s, and the arc current for melting the intermediate alloy is 200 - 250 A. After mixing the two intermediate alloys, the number of melting times is 8 - 10 times to ensure uniform composition, the arc current is 200 - 250 A, and the melting time for each time is 180 s.
[0032] Example 2
[0033] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNbCu 0.2 .
[0034] The preparation method of the TiZrHfNbCu 0.2 high-entropy alloy:
[0035] After weighing Ti, Zr, Hf, Nb, and Cu with a purity of 99.9% according to a molar ratio of 1:1:1:1:0.2, vacuum argon arc melting is used to obtain a copper-containing antibacterial high-entropy alloy. Specifically: Ti, Zr, and Cu are stacked together for vacuum argon arc melting to obtain a Ti-Zr-Cu intermediate alloy; Hf and Nb are stacked together and vacuum argon arc melted to obtain an Hf-Nb intermediate alloy; the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy are stacked together and vacuum argon arc melted to obtain the high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. When preparing the Ti-Zr-Cu master alloy ingot, the number of flipping and melting times is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 180 - 200 A. When preparing the Hf-Nb master alloy ingot, the number of flipping and melting times is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 200 - 250 A. After mixing the two master alloys, the melting times are 8 - 10 times to ensure uniform composition, the arc current is 200 - 250 A, and the melting time for each time is 180 s.
[0036] Example 3
[0037] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNbCu 0.4 .
[0038] The preparation method of this TiZrHfNbCu 0.4 high-entropy alloy is as follows:
[0039] After weighing Ti, Zr, Hf, Nb, and Cu with a purity of 99.9% according to a molar ratio of 1:1:1:1:0.4, vacuum argon arc melting is used to obtain a copper-containing antibacterial high-entropy alloy. Specifically: Ti, Zr, and Cu are stacked together and subjected to vacuum argon arc melting to obtain a Ti-Zr-Cu master alloy; Hf and Nb are stacked together and vacuum argon arc melted to obtain an Hf-Nb master alloy; the Ti-Zr-Cu master alloy and the Hf-Nb master alloy are stacked together and vacuum argon arc melted to obtain a high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3 Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. When preparing the Ti-Zr-Cu master alloy ingot, the number of flipping and melting times is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 180 - 200 A. When preparing the Hf-Nb master alloy ingot, the number of flipping and melting times is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 200 - 250 A. After mixing the two master alloys, the melting times are 8 - 10 times to ensure uniform composition, the arc current is 200 - 250 A, and the melting time for each time is 180 s.
[0040] Example 4
[0041] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNbCu 0.6 .
[0042] The preparation method of this TiZrHfNbCu 0.6 high-entropy alloy is as follows:
[0043] After weighing Ti, Zr, Hf, Nb and Cu with a purity of 99.9% according to a molar ratio of 1:1:1:1:0.6, vacuum argon arc melting is adopted to obtain a copper-containing antibacterial high-entropy alloy. Specifically: Stack Ti, Zr and Cu together and carry out vacuum argon arc melting to obtain a Ti-Zr-Cu intermediate alloy; Stack Hf and Nb together and carry out vacuum argon arc melting to obtain an Hf-Nb intermediate alloy; Stack the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy together and carry out vacuum argon arc melting to obtain a high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3 Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. The number of times of flipping and melting for the Ti-Zr-Cu intermediate alloy ingot during preparation is 5-6 times, the melting time for each time is 180 s, and the arc current is 180-200 A. The number of times of flipping and melting for the Hf-Nb intermediate alloy ingot during preparation is 5-6 times, the melting time for each time is 180 s, and the arc current is 200-250 A. After the two intermediate alloys are mixed, the number of melting times is 8-10 times to ensure uniform composition, the arc current is 200-250 A, and the melting time for each time is 180 s.
[0044] Example 5
[0045] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNbCu 0.8 .
[0046] The preparation method of this TiZrHfNbCu 0.8 high-entropy alloy is as follows:
[0047] After weighing Ti, Zr, Hf, Nb and Cu with a purity of 99.9% according to a molar ratio of 1:1:1:1:0.8, vacuum argon arc melting is adopted to obtain a copper-containing antibacterial high-entropy alloy. Specifically: Stack Ti, Zr and Cu together and carry out vacuum argon arc melting to obtain a Ti-Zr-Cu intermediate alloy; Stack Hf and Nb together and carry out vacuum argon arc melting to obtain an Hf-Nb intermediate alloy; Stack the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy together and carry out vacuum argon arc melting to obtain a high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. When preparing the Ti-Zr-Cu master alloy ingot, the number of times of turning and melting is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 180 - 200 A. When preparing the Hf-Nb master alloy ingot, the number of times of turning and melting is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 200 - 250 A. After mixing the two master alloys, the number of melting times is 8 - 10 times to ensure uniform composition, the arc current is 200 - 250 A, and the melting time for each time is 180 s.
[0048] Example 6
[0049] In this example, the molecular formula of the TiZrHfNbCu high-entropy alloy is TiZrHfNbCu.
[0050] The preparation method of the TiZrHfNbCu high-entropy alloy is as follows:
[0051] After weighing Ti, Zr, Hf, Nb, and Cu with a purity of 99.9% according to a molar ratio of 1:1:1:1:1, vacuum argon arc melting is used to obtain a copper-containing antibacterial high-entropy alloy. Specifically: Ti, Zr, and Cu are stacked together for vacuum argon arc melting to obtain a Ti-Zr-Cu master alloy; Hf and Nb are stacked together for vacuum argon arc melting to obtain an Hf-Nb master alloy; the Ti-Zr-Cu master alloy and the Hf-Nb master alloy are stacked together for vacuum argon arc melting to obtain a high-entropy alloy. During the vacuum argon arc melting process, the vacuum in the cavity is pumped to 4.5×10 -3 Pa, and then argon is filled to 0.02 MPa to avoid oxidation during the alloy melting process. When preparing the Ti-Zr-Cu master alloy ingot, the number of times of turning and melting is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 180 - 200 A. When preparing the Hf-Nb master alloy ingot, the number of times of turning and melting is 5 - 6 times, the melting time for each time is 180 s, and the arc current is 200 - 250 A. After mixing the two master alloys, the number of melting times is 8 - 10 times to ensure uniform composition, the arc current is 200 - 250 A, and the melting time for each time is 180 s.
[0052] The prepared high-entropy alloy is respectively tested for its microstructure, antibacterial property, cytotoxicity, and mechanical property:
[0053] (1) Material characterization of the high-entropy alloy
[0054] 1. X-ray diffraction (XRD) test
[0055] The alloy ingot obtained by melting was cut into small square pieces of 10 mm×10 mm×2 mm using wire electrical discharge machining, and then the surface of the samples was polished smoothly using sandpapers of 240#, 600#, 1000#, 1500# and 2000# in sequence. The surface of the prepared samples was scanned using an X-ray diffractometer at a scanning angle from 10° to 100° with a scanning step of 2° / min. Figure 1 For the X-ray diffraction results of the high-entropy alloys in Examples 1 to 6, the result analysis found that the TiZrHfNb alloy was a BCC phase, and after doping with Cu element, a copper-rich phase precipitated in the alloy.
[0056] 2. Observation by high-resolution field emission scanning electron microscope
[0057] After the alloy ingot was cut into square pieces of 10 mm×10 mm×2 mm using wire cutting, the surface of the samples was polished smoothly using sandpapers of 240#, 600#, 1000#, 1500# and 2000# in sequence, and then the surface of the samples was polished using alumina polishing solutions of 3, 1, 0.05 microns until there were no obvious scratches.
[0058] Figure 2 SEM images of the antibacterial high-entropy alloys prepared in Examples 1 to 6; a to f correspond to Examples 1 to 6 respectively.
[0059] (2) Determination of antibacterial performance:
[0060] After the alloy was cut into square pieces of 10 mm×10 mm×2 mm, the four sides of the samples were polished smoothly using sandpapers of 240#, 600#, 1000#, 1500# and 2000# in sequence. The samples were irradiated under ultraviolet light for 30 min for sterilization. The Staphylococcus epidermidis used in the experiment was activated and cultured in advance. The alloys prepared in Examples 1 to 6 were co-cultured with Staphylococcus epidermidis for 24 hours under the conditions of 90% RH and 37°C, and the results of dilution plate coating were as Figure 3 , and the results showed that: Examples 5 - 6 showed antibacterial properties against Staphylococcus epidermidis. Among them, the antibacterial rate of Example 5 was 84%, and the antibacterial rate of Example 6 was 98%.
[0061] Figure 3 Results of plate coating after co-culturing the antibacterial high-entropy alloys prepared in Examples 1 to 6 with Staphylococcus epidermidis for 24 h.
[0062] (3) Cell proliferation detection:
[0063] After cutting the alloy into square slices with dimensions of 10 mm × 10 mm × 2 mm, the four sides of the samples were then polished smoothly using sandpapers of 240#, 600#, 1000#, 1500#, and 2000# in sequence. The samples were irradiated under ultraviolet light for 30 min for sterilization, and then according to the standards such as "GB / T 16886.5-2017 Biological evaluation of medical devices - Part 5: Tests for in vitro cytotoxicity", the extraction solution of the samples was prepared, and then the extraction solution was co-cultured with immortalized human umbilical vein endothelial cells for 24 h. Cell Counting Kit-8 (CCK-8) reagent was added to detect the cell proliferation. The absorbance of the samples at 450 nm was measured using an enzyme-linked immunosorbent assay (ELISA) reader, and the results were obtained as Figure 4 shown. The absorbances of Examples 2-6 were all higher than those of Example 1 and the blank control group, indicating that the addition of Cu element did not reduce the biocompatibility of the alloy. Figure 4 Figure showing the line graph of the absorbance values at 450 nm after co-culturing the antibacterial high-entropy alloys with different Cu contents prepared in Examples 1-6 with human umbilical vein endothelial cells for 24 h;
[0064] (4) Room temperature compression experiment
[0065] The alloy ingot was cut into small cylinders with a diameter of 3 mm and a height of 4.5 mm. The upper and lower surfaces of the cylinders were polished smoothly and parallel using sandpaper. A universal testing machine was used to conduct room temperature compression experiments on Examples 1-6. The compression rate was 10 -3 s -1 , and the compression stress-strain curves of the alloy at room temperature were obtained as Figure 5 shown. As the applied stress increased, the alloy samples first underwent elastic deformation, then plastic deformation after reaching the yield strength, and fracture occurred when the plastic strain reached a certain value. By comparing the slopes of the elastic deformation segments of the stress-strain curves of Examples 1-6, the following results were obtained: the Young's moduli of Examples 1-6 did not change significantly with the change of Cu content.
[0066] Figure 5 Figure showing the compression stress-strain curves of the antibacterial high-entropy alloys prepared in Examples 1-6 at room temperature.
Claims
1. A biomedical antibacterial high-entropy alloy TiZrHfNbCu, characterized in that: Composed of five elements, Ti, Zr, Hf, Nb, and Cu, with the composition of TiZrHfNbCu x , where 0 < x ≤ 1.2, and the molar ratio of Ti, Zr, Hf, Nb, and Cu is 1:1:1:1:x; The biomedical antibacterial high-entropy alloy TiZrHfNbCu is prepared by the following method: Mix and melt Ti, Zr, and Cu to obtain a Ti-Zr-Cu intermediate alloy; mix and melt Hf and Nb to obtain an Hf-Nb intermediate alloy; mix and melt the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy to obtain an antibacterial high-entropy alloy.
2. The biomedical antibacterial high-entropy alloy TiZrHfNbCu according to claim 1, characterized in that: x is 0.7 to 1.
2.
3. The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to any one of claims 1 to 2, characterized in that: Mix Ti, Zr, and Cu and carry out vacuum argon arc melting to obtain a Ti-Zr-Cu intermediate alloy; mix Hf and Nb and carry out vacuum argon arc melting to obtain an Hf-Nb intermediate alloy; mix the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy, and carry out vacuum argon arc melting to obtain an antibacterial high-entropy alloy.
4. The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to claim 3, characterized in that: The melting conditions of the Ti-Zr-Cu intermediate alloy: the arc current is 180 to 200 A, the melting time per time is 180 s; the number of times of flipping and melting is 5 to 6 times; The melting conditions of the Hf-Nb intermediate alloy: the arc current is 200 to 250 A, the melting time per time is 180 s, and the number of times of flipping and melting is 5 to 6 times; The conditions for mixing the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy and carrying out vacuum argon arc melting: The arc current is 200 to 250 A, the melting time per time is 180 s; the number of melting times is 8 to 10 times.
5. The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to claim 3, wherein: During the vacuum argon arc melting process, the vacuum in the cavity is pumped to a vacuum degree of ≤ 4.5×10 -3 Pa, and then argon gas is filled to 0.02 Pa.
6. The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to claim 3, characterized in that: The content of each of the five raw material particles of Ti, Zr, Hf, Nb, and Cu is 99.9%; After the melting of the Ti-Zr-Cu intermediate alloy and the Hf-Nb intermediate alloy is completed, cooling is carried out.
7. The preparation method of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to claim 6, wherein: The cooling method is water cooling for 10 - 20 min.
8. Use of the biomedical antibacterial high-entropy alloy TiZrHfNbCu according to any one of claims 1 to 2, characterized in that: The biomedical antibacterial high-entropy alloy TiZrHfNbCu is used to prepare medical implant materials.