Zinc-containing antibacterial corrosion-resistant CoCrCuFeNiZn high-entropy alloy and preparation method thereof

Abstract

The invention provides a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy, which is composed of six elements of Co, Cr, Cu, Fe, Ni and Zn, and the mass percentage range of the six elements is as follows: (20 wt%) of Co, (20 wt%) of Cr, (20 wt%) of Fe, (20 wt%) of Ni, (19-19.9 wt%) of Cu and (0.1-1 wt%) of Zn, and the mass percentage range of the six elements is as follows: (20 wt%) of Co, (20 wt%) of Cr, (20 wt%) of Fe, (20 wt%) of Fe, (20 wt%) of Ni, (19-19.9 wt%) of Ni and (0.1-1 wt%) of Zn. According to the CoCrCuFeNiZn high-entropy alloy disclosed by the invention, the zinc element is introduced and has a synergistic effect with the copper element, so that the CoCrCuFeNiZn high-entropy alloy is endowed with an unprecedented antibacterial effect, and bacterial growth and biofilm formation are effectively inhibited.

Description

Technical Field

[0001] The present invention relates to the field of metallic materials, and particularly to a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy and a preparation method thereof. Background Art

[0002] Traditional alloy materials play an important role in many fields. However, in some specific application scenarios, they face the dual challenges of corrosion resistance and antibacterial performance. In the medical industry, alloy materials need to have good antibacterial performance to prevent bacterial infections; in fields such as ocean engineering and chemical engineering, alloy materials need excellent corrosion resistance to cope with harsh environments. However, the alloy materials on the market often have difficulty meeting these requirements simultaneously.

[0003] In order to improve the antibacterial performance of alloys, researchers have tried to introduce antibacterial elements such as silver and copper. Although these attempts have achieved certain results, there are still some problems, such as unstable antibacterial effects and a decline in mechanical properties. At the same time, improving the corrosion resistance of alloys is also an urgent problem to be solved. In a corrosive environment, alloy materials are easily eroded, resulting in a decline in performance and even failure.

[0004] Therefore, the development of a new alloy material that simultaneously has excellent antibacterial performance and corrosion resistance and whose mechanical properties are not affected has always been a research hotspot and difficulty in the field of materials science. Summary of the Invention

[0005] Under this background condition, the present invention proposes a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy and a preparation method thereof. Through a unique element ratio and an advanced preparation process, the antibacterial performance and corrosion resistance are successfully solved without affecting the mechanical properties of the alloy.

[0006] On the one hand, the present invention provides a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy. The CoCrCuFeNiZn high-entropy alloy is composed of six elements, namely Co, Cr, Cu, Fe, Ni, and Zn. The mass percentage range of the six elements is: Co (20 wt.%), Cr (20 wt.%), Fe (20 wt.%), Ni (20 wt.%), Cu (19 - 19.9 wt.%), and Zn (0.1 - 1 wt.%). By cleverly introducing the zinc element and cooperating with the copper element, the alloy is given unprecedented antibacterial efficacy, effectively inhibiting bacterial growth and biofilm formation.

[0007] Furthermore, the structure of the CoCrCuFeNiZn high-entropy alloy is a single-phase FCC, having strong corrosion resistance and strong antibacterial performance.

[0008] The second aspect of the present invention also provides a preparation method of a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy, specifically as follows:

[0009] S1 Vacuum melting: According to the mass percentages of the six elements, accurately weigh and put them into a vacuum induction melting furnace. After evacuating the air, fill it with inert gas for protection, adjust the induction current to completely melt the elements, keep them in a liquid state for a period of time, and then pour them into a graphite mold to form an alloy ingot;

[0010] S2 Rolling treatment: Anneal the alloy ingot at a high temperature, then cut it into squares, and perform multi-pass rolling treatment at room temperature using a two-roll rolling mill;

[0011] S3 Multiple heat treatments: After rolling is completed, perform multiple heat treatments on the alloy material to obtain a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy.

[0012] Further, in the step S1, evacuate the air to be lower than 5×10 -5 Pa.

[0013] Further, in the step S1, the magnitude of the induction current is 200 - 600 A.

[0014] Further, in the step S2, the annealing temperature is 1200 °C and the annealing time is 12 h.

[0015] Further, in the step S2, room temperature rolling is adopted, and the rolling deformation is 70 - 80%.

[0016] Further, in the step S3, the multiple heat treatments are specifically three-stage heat treatments. The first-stage high-temperature diffusion treatment is at 1000 °C - 1050 °C for 2 h to eliminate rolling stress and reduce composition segregation; the second-stage medium-temperature treatment is at 600 °C - 700 °C for 1 h to form nano-precipitation phases; the third-stage heat treatment is at 400 °C - 500 °C for 0.5 h to eliminate thermal stress and stabilize the microstructure.

[0017] The beneficial effects of the present invention are as follows: The zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy provided by the present invention has excellent antibacterial and antiviral properties by innovatively introducing a specific proportion of zinc element. Zinc is relatively inexpensive and has a low cost, and is suitable for fields such as household products and automobiles. While utilizing the antibacterial and antiviral properties brought by the zinc element, the present invention actively improves the content of each element and optimizes the key links in the processing process, so that the mechanical properties and corrosion resistance of the alloy are significantly improved, meeting the requirements of various application scenarios. Brief Description of the Drawings

[0018] The present invention will be further described below in conjunction with the drawings and embodiments.

[0019] Figure 1 The polarization curve of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy in Example 1;

[0020] Figure 2 The polarization curve of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy in Example 2;

[0021] Figure 3 The metallographic structure diagram of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy in Example 3;

[0022] Figure 4 The SEM of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy in Example 4. Detailed implementation manners

[0023] Before discussing the exemplary embodiments in more detail, it should be noted that some exemplary embodiments are described as processes or methods depicted as flowcharts. Although the flowcharts describe the operations as sequential processes, many of the operations can be implemented in parallel, concurrently, or simultaneously. In addition, the order of the operations can be rearranged. The process can be terminated when its operations are completed, but it can also have additional steps not included in the drawings. The process can correspond to a method, function, procedure, subroutine, subprogram, and the like.

[0024] It should be understood that although terms such as "first" and "second" may be used herein to describe various units, these units should not be limited by these terms. These terms are only used to distinguish one unit from another. For example, without departing from the scope of the exemplary embodiments, the first unit can be called the second unit, and similarly, the second unit can be called the first unit. The term "and / or" used herein includes any and all combinations of one or more of the listed associated items.

[0025] The chemical reagents used in the embodiments of the present invention are all ordinary commercially available analytical pure reagents without special instructions.

[0026] The purity of the elemental raw materials used in the embodiments of the present invention is greater than 99.99%.

[0027] The present invention provides a preparation method of a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy, including

[0028] S1 Vacuum Melting: Weigh accurately according to the mass percentages of the six elements, put them into a vacuum induction melting furnace. After evacuating the air, fill it with inert gas for protection, adjust the induction current to completely melt the elements. After maintaining the liquid state for a period of time, pour it into a graphite mold to form an alloy ingot. Preferably, evacuate the air to a pressure lower than 5×10-5Pa; the magnitude of the induction current is 200 - 600A.

[0029] S2 Rolling Treatment: Anneal the alloy ingot at a high temperature, and then cut it into blocks. Conduct multi-pass rolling treatment at room temperature using a two-roll rolling mill. Preferably, the annealing temperature is 1200°C and the annealing time is 12h; conduct rolling at room temperature, and the rolling deformation is 70 - 80%.

[0030] S3 Multiple Heat Treatments: After rolling is completed, conduct multiple heat treatments on the alloy material. Preferably, the multiple heat treatments are specifically three-stage heat treatments. The first-stage is high-temperature diffusion treatment at 1000°C - 1050°C for 2h to eliminate rolling stress and reduce composition segregation; the second-stage is medium-temperature treatment at 600°C - 700°C for 1h to form nano-precipitation phases; the third-stage heat treatment is at 400°C - 500°C for 0.5h to eliminate thermal stress and stabilize the microstructure.

[0031] Example 1

[0032] S1 Vacuum Melting: Weigh accurately six metallic elements of Co (20wt.%), Cr (20wt.%), Fe (20wt.%), Ni (20wt.%), Cu (19.9wt.%), and Zn (0.1wt.%) according to the ratio, and put them into a vacuum induction melting furnace. Evacuate the air until the vacuum degree in the furnace cavity is lower than 1×10 -5 Pa, fill it with argon for protection, adjust the induction current to 400A to completely melt the elements. After maintaining the liquid state for 10 minutes, pour it into a graphite mold to form an alloy ingot.

[0033] S2 Rolling Treatment: Anneal the ingot at 1200°C for 12 hours, and then cut it into blocks. Conduct multi-pass rolling treatment at room temperature using a two-roll rolling mill, and the final rolling amount is 80%.

[0034] S3 Multiple Heat Treatments: The first-stage is high-temperature diffusion treatment at a temperature of 1000°C for 2 hours; the second-stage is medium-temperature treatment at a temperature of 600°C for 1 hour; the third-stage heat treatment is at a temperature of 400°C for 0.5 hours to obtain a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy.

[0035] After testing, Figure 1The polarization curve of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy electrode. The corrosion potential of the low-cost, high-strength zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy is -0.31 V, and the corrosion current density is 5.48×10 -5 A·cm -2 . The antibacterial rate against Staphylococcus aureus reaches 98.9%, and the antibacterial rate against Escherichia coli reaches 99.1%.

[0036] Example 2

[0037] S1 Vacuum melting: Accurately weigh six metal elements of Co (20 wt.%), Cr (20 wt.%), Fe (20 wt.%), Ni (20 wt.%), Cu (19.7 wt.%), and Zn (0.3 wt.%) according to the ratio, and put them into a vacuum induction melting furnace. Evacuate to a vacuum degree in the furnace cavity lower than 1×10 -5 Pa, fill with argon for protection, adjust the induction current to 400 A to completely melt the elements. After maintaining the liquid state for 10 minutes, pour it into a graphite mold to form an alloy ingot.

[0038] S2 Rolling treatment: Anneal the ingot at 1200 °C for 12 hours, then cut it into squares, and perform multi-pass rolling treatment at room temperature using a two-roll mill. The final rolling reduction is 80%.

[0039] S3 Multiple heat treatments: The first-stage high-temperature diffusion treatment, the temperature is 1000 °C, and the holding time is 2 hours; the second-stage medium-temperature treatment, the temperature is 600 °C, and the holding time is 1 hour; the third-stage heat treatment, the temperature is 400 °C, and the holding time is 0.5 hours to obtain the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy.

[0040] After testing, Figure 2 The polarization curve of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy electrode. The corrosion potential of the low-cost, high-strength zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy is -0.38 V, and the corrosion current density is 5.17×10 -5 A·cm -2 . The antibacterial rate against Staphylococcus aureus reaches 99.4%, and the antibacterial rate against Escherichia coli reaches 99.3%.

[0041] Example 3

[0042] S1 Vacuum melting: Weigh accurately six metal elements, Co (20 wt.%), Cr (20 wt.%), Fe (20 wt.%), Ni (20 wt.%), Cu (19.5 wt.%), and Zn (0.5 wt.%) according to the ratio, and put them into a vacuum induction melting furnace. Evacuate to a vacuum degree in the furnace cavity lower than 1×10-5 Pa, fill with argon for protection, adjust the induction current to 400 A to completely melt the elements. After maintaining the liquid state for 10 minutes, pour it into a graphite mold to form an alloy ingot.

[0043] S2 Rolling treatment: Anneal the ingot at 1200 °C for 12 hours, then cut it into squares, and perform multi-pass rolling treatment at room temperature using a two-roll mill. The final rolling reduction is 80%.

[0044] S3 Multiple heat treatments: The first-stage high-temperature diffusion treatment at a temperature of 1000 °C for 2 hours; the second-stage medium-temperature treatment at a temperature of 600 °C for 1 hour; the third-stage heat treatment at a temperature of 400 °C for 0.5 hours to obtain a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy.

[0045] After testing, the corrosion potential of the low-cost, high-strength, zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy is -0.41 V, and the corrosion current density is 5.13*10 -5 A·cm -2 . The antibacterial rate against Staphylococcus aureus reaches 99.3%, and the antibacterial rate against Escherichia coli reaches 99.5%. Figure 3 is the metallographic structure diagram of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy. The grains are irregular polygons, evenly distributed, and the grain boundaries are clear; the grain sizes are relatively consistent, without obvious coarsening or abnormal growth.

[0046] Example 4

[0047] S1 Vacuum melting: Weigh accurately six metal elements, Co (20 wt.%), Cr (20 wt.%), Fe (20 wt.%), Ni (20 wt.%), Cu (19 wt.%), and Zn (1 wt.%) according to the ratio, and put them into a vacuum induction melting furnace. Evacuate to a vacuum degree in the furnace cavity lower than 1×10-5 Pa, fill with argon for protection, adjust the induction current to 400 A to completely melt the elements. After maintaining the liquid state for 10 minutes, pour it into a graphite mold to form an alloy ingot.

[0048] S2 Rolling treatment: Anneal the ingot at 1200 °C for 12 hours, then cut it into squares, and perform multi-pass rolling treatment at room temperature using a two-roll mill. The final rolling reduction is 80%.

[0049] S3 Multi-stage heat treatment: The first-stage high-temperature diffusion treatment is carried out at a temperature of 1000 °C for 2 hours; the second-stage medium-temperature treatment is carried out at a temperature of 600 °C for 1 hour; the third-stage heat treatment is carried out at a temperature of 400 °C for 0.5 hour to obtain a zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy.

[0050] After testing, the corrosion potential of the low-cost, high-strength, zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy is -0.5 V, and the corrosion current density is 4.98*10 -5 A·cm -2 . The antibacterial rate against Staphylococcus aureus reaches 99.6%, and the antibacterial rate against Escherichia coli reaches 99.7%. Figure 4 Figure is the SEM of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy, clearly showing the metallographic microstructure of the invented alloy.

[0051] Comparative Example 1

[0052] Comparative Example 1 is the same as Example 4, except that the composition is different. Zinc element is not contained in Comparative Example 1. In order to maintain the overall composition balance of the alloy, the content of copper is adjusted to 20 wt%, and the ratios of Co, Cr, Fe, and Ni elements remain the same as in Example 4, still 20 wt% each. During the preparation process, the operations of vacuum melting, rolling treatment, and multi-stage heat treatment steps in Example 4 are still carried out. After testing, the corrosion potential of this alloy is -0.63 V, and the corrosion current density 2 is 6.96*10 -5 A·cm -2 . The antibacterial rate against Staphylococcus aureus reaches 90.3%, and the antibacterial rate against Escherichia coli reaches 91.2%. It can be seen from the data that due to the lack of zinc element, the antibacterial and corrosion-resistant properties of the alloy are degraded compared with Example 4. The lack of zinc element leads to the degradation of the antibacterial and corrosion-resistant properties of the alloy. The main reasons are as follows: The antibacterial effect of zinc ions (Zn 2+ ) depends on its penetration of the bacterial cell membrane, interference with the activity of metabolic enzymes, and cooperation with copper element to enhance the continuous bactericidal ability. The lack of zinc will reduce the ion release and the generation of reactive oxygen species, weakening the antibacterial effect; at the same time, zinc improves the corrosion resistance through mechanisms such as sacrificial anode protection, formation of a dense zinc oxide passivation film, and refinement of grains to reduce the corrosion active points. When zinc is lacking, the alloy loses electrochemical protection, the passivation film is incomplete and the microstructure is coarsened, accelerating the corrosion process. The multiple functions of zinc make it difficult to be replaced in the synergistic system, and its lack directly leads to the synchronous degradation of the two properties.

[0053] Comparative Example 2

[0054] Comparative Example 2 is the same as Example 4, except that the rolling reduction is different. When rolling the ingot, Comparative Example 2 uses a two-roll mill to perform multi-pass rolling at room temperature, and the final rolling reduction is 40%, rather than 80% in Example 4. In terms of element ratio, vacuum melting, and multiple heat treatment steps, it is consistent with Example 4. After testing, the corrosion potential of this alloy is -0.59V, and the corrosion current density is 6.55*10 -5 A·cm -2 , the antibacterial rate against Staphylococcus aureus reaches 95.0%, and the antibacterial rate against Escherichia coli reaches 95.9%. Comparing with Example 4, it can be seen that the reduction of rolling reduction reduces the antibacterial and corrosion resistance performance of the alloy, indicating that the rolling reduction has an important impact on the alloy performance.

[0055] Comparative Example 3

[0056] Comparative Example 3 is the same as Example 4, except that the temperature of the first heat treatment is different. In the multiple heat treatment process, the temperature of the first-stage high-temperature diffusion treatment in Comparative Example 3 is 800°C, and the holding time is still 2 hours. The remaining second-stage medium-temperature treatment (600°C, holding for 1 hour) and the third-stage heat treatment (400°C, holding for 0.5 hour) are consistent with Example 4, and the element ratio and other steps of the preparation process are also the same. After testing, the corrosion potential of this alloy is -0.68V, and the corrosion current density is 5.80*10 -5 A·cm -2 , the antibacterial rate against Staphylococcus aureus reaches 95.4%, and the antibacterial rate against Escherichia coli reaches 96.5%. Compared with Example 4, the lower temperature of the first heat treatment causes certain changes in the alloy performance, indicating that the temperature of the first heat treatment plays a key role in optimizing the alloy performance.

[0057] Comparative Example 4

[0058] Comparative Example 4 is the same as Example 4, except that the temperature of the second heat treatment is different. In the multiple heat treatment process, the temperature of the second-stage medium-temperature treatment in Comparative Example 4 is 500°C, and the holding time is 1 hour. The first-stage high-temperature diffusion treatment (1000°C, holding for 2 hours), the third-stage heat treatment (400°C, holding for 0.5 hour), and the element ratio and other steps of the preparation process are the same as those in Example 4. After testing, the corrosion potential of this alloy is -0.64V, and the corrosion current density is 5.50*10 -5 A·cm -2 , the antibacterial rate against Staphylococcus aureus reaches 96.7%, and the antibacterial rate against Escherichia coli reaches 97.4%. Compared with Example 4, after changing the temperature of the second heat treatment, the alloy performance has changed, indicating that the temperature of the second heat treatment has a significant impact on the microstructure and performance of the alloy.

[0059] Comparative Example 5

[0060] Comparative Example 5 is the same as Example 4, except that the third heat treatment temperature is different. In the multiple heat treatment steps, the third-stage heat treatment temperature of Comparative Example 5 is 300 °C, and it is held for 0.5 hours. The first-stage high-temperature diffusion treatment (1000 °C, held for 2 hours), the second-stage medium-temperature treatment (600 °C, held for 1 hour), the element ratio, and other aspects of the preparation process are the same as those of Example 4. After testing, the corrosion potential of this alloy is -0.57 V, and the corrosion current density is 5.21*10 -5 A·cm -2 , the antibacterial rate against Staphylococcus aureus reaches 98.0%, and the antibacterial rate against Escherichia coli reaches 98.6%. It can be seen that the reduction of the third heat treatment temperature has an impact on the alloy performance, indicating that the third heat treatment is of great significance in stabilizing the alloy structure and improving the performance.

[0061] The following table is a summary chart of the test results of Examples 1 to 4 and Comparative Examples 1 to 5.

[0062]

[0063] It can be found from Comparative Example 1 that the added zinc element in the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy provided by the present invention greatly improves the antibacterial performance and corrosion resistance; it can be found from Comparative Examples 2 to 5 that the rolling process, the requirements for the rolling amount, and the conditions of multiple heat treatments in the preparation method of the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high-entropy alloy provided by the present invention all greatly improve the antibacterial performance and corrosion resistance. In addition, zinc metal is cheaper than other precious metals, has rich mineral resources, and has low preparation costs, which is conducive to large-scale promotion in the construction industry and the automotive industry.

[0064] The above are only the embodiments of the present invention. Specific structures and common knowledge such as characteristics that are well known in the art are not described in detail here. Those of ordinary skill in the art know all the common technical knowledge in the technical field to which the invention belongs before the application date or the priority date, can know all the existing technologies in this field, and have the ability to apply the conventional experimental means before this date. Those of ordinary skill in the art can, under the inspiration given in this application, combine their own abilities to improve and implement this solution. Some typical well-known structures or well-known methods should not become obstacles for those of ordinary skill in the art to implement this application. It should be noted that for those skilled in the art, without departing from the structure of the present invention, several deformations and improvements can still be made, and these should also be regarded as the protection scope of the present invention, and these will not affect the implementation effect of the present invention and the practicality of the patent. The protection scope required by this application should be based on the content of its claims, and the specific implementation manners described in the specification can be used to interpret the content of the claims.

Claims

1. A zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy, characterized in that: The CoCrCuFeNiZn high entropy alloy is composed of six elements: Co, Cr, Cu, Fe, Ni and Zn, and the mass percentages of the six elements are: Co (20wt.%), Cr (20wt.%), Fe (20wt.%), Ni (20wt.%), Cu (19-19.9wt.%) and Zn (0.1-1wt.%).

2. The zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 1, characterized in that: The CoCrCuFeNiZn high entropy alloy has a single-phase FCC structure.

3. A method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to any one of claims 1 to 2, comprising the following steps: S1 Vacuum melting: according to the mass percentage of the six elements, accurately weigh them, put them into a vacuum induction melting furnace, evacuate them, fill them with inert gas protection, adjust the induction current, melt the elements completely, keep them in liquid state for a period of time, and then pour them into a graphite mold to form an alloy ingot; S2 rolling treatment: the alloy ingot is annealed at high temperature, then cut into blocks, and subjected to multiple rolling treatments at room temperature using a twin-roll mill; S3 Multiple heat treatment: After rolling, the alloy material is subjected to multiple heat treatments to obtain zinc-containing, antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy.

4. The method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 3, characterized in that: In step S1, the vacuum is evacuated to less than 5×10 -5 Pa.

5. The method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 3, characterized in that: In the step S1, the magnitude of the induced current is 200-600A.

6. The method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 3, characterized in that: In step S2, the annealing temperature is 1200° C. and the annealing time is 12 hours.

7. The method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 3, characterized in that: In the step S2, room temperature rolling is adopted, and the rolling deformation is 70-80%.

8. The method for preparing the zinc-containing antibacterial and corrosion-resistant CoCrCuFeNiZn high entropy alloy according to claim 3, characterized in that: In step S2, the multiple heat treatment is specifically a three-stage heat treatment, the first stage is a high-temperature diffusion treatment at 1000°C to 1050°C, and the heat preservation is 2 hours; the second stage is a medium-temperature treatment at 600°C to 700°C, and the heat preservation is 1 hour; the third stage is a heat treatment at 400°C to 500°C, and the heat preservation is 0.5 hours.

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