CN118207464B - Entropy alloy material for promoting bone TiZrCoCrMoCu to resist bacteria and preparation method thereof - Google Patents

Abstract

The invention relates to an entropy alloy material for promoting bone TiZrCoCrMoCu to be antibacterial and a preparation method thereof, belonging to the technical field of antibacterial materials. According to the invention, a CoCrMo intermediate alloy is prepared firstly by a vacuum smelting technology, then smelting power and time are adjusted according to the atomic fraction of Cu in the antibacterial intermediate alloy to prepare A alloy particles, zr particles are added after mixing, and smelting is carried out for more than two times after pretreatment, so as to obtain TiZrCoCrMoCu alloy. The chemical formula of the alloy material is Ti _aZr_bCo_cCr_dMo_eCu_f (at.%), wherein 33< a is less than or equal to 45, 33< b is less than or equal to 45, 11< c is less than or equal to 15,5< d is less than or equal to 10,0.5< e is less than or equal to 2, and 0 < f is less than or equal to 10. The preparation process of the invention is simpler, complex heat treatment is not needed, the melting point of the alloy is reduced, the casting performance is improved, and the cost is effectively reduced.

Description

A bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material and preparation method thereof

Technical Field

The invention belongs to the technical field of antibacterial materials, and particularly relates to an osteogenic TiZrCoCrMoCu antibacterial medium-entropy alloy material and a preparation method thereof.

Background technique

Bone problems, such as fractures, bone defects, and joint diseases, greatly reduce people's health and quality of life. Bone repair implant surgery is a common strategy in orthopedic medicine to treat these diseases. However, the long-term stability, biocompatibility, and prevention of postoperative infection of bone repair implants remain key issues that need to be addressed.

In the field of orthopedic implants, commonly used materials include stainless steel, cobalt-chromium-molybdenum (CoCrMo) alloys, and titanium (Ti) alloys. Thanks to its excellent biocompatibility, corrosion resistance, high strength, and low elastic modulus (between 80 GPa and 160 GPa), titanium alloys have gradually become the preferred choice of metal implant materials. In contrast, the elastic modulus of stainless steel 316L and Co-Cr-Mo alloys are both over 200 GPa, much higher than that of titanium alloys. The lower elastic modulus of titanium alloys makes the stress between the implant and the bone tissue more evenly distributed, which helps to reduce the bone absorption and implant loosening caused by the "stress shielding" phenomenon. However, the defects of titanium alloy implants cannot be ignored: First, the existing low elastic modulus titanium alloys usually contain high melting point and expensive metal elements such as niobium (Nb) and tantalum (Ta), which leads to high preparation costs. Secondly, titanium alloys have poor wear resistance. In the physiological environment of the human body, due to problems such as friction corrosion, tiny metal particles are released, causing inflammation of the surrounding tissues and affecting the health of patients. Although CoCrMo alloy has a higher elastic modulus compared to titanium alloy, its excellent wear resistance ensures its stability in long-term use.

The above-mentioned traditional orthopedic implant materials are widely used in medical practice and have achieved remarkable results, but the lack of antibacterial properties limits their development in the implant field. At present, the global waste of medical resources and treatment costs caused by postoperative bacterial infections each year cannot be ignored. When the implant material does not have antibacterial function, patients are more susceptible to bacterial infection after surgery, which in turn causes the implant to loosen or even fall off, ultimately causing the patient to suffer a double loss of health and money. Therefore, the development and research of bone repair implant materials with good antibacterial properties is of great significance to reduce the risk of postoperative infection and improve the long-term success rate of implants.

Based on the above background, a new type of antibacterial medium-entropy alloy, TiZrCoCrMoCu alloy, was successfully developed by combining the advantages of CoCrMo alloy and titanium alloy, and adding titanium (Ti), zirconium (Zr) elements and copper (Cu) elements with antibacterial properties. TiZrCoCrMoCu alloy has the low modulus and high biocompatibility of Ti alloy, and also obtains the high wear resistance of CoCr alloy. In view of the problem that CoCr alloy slowly releases Co and Cr ions during long-term use, the alloy reduces the content of Co and Cr elements, and utilizes the hysteresis diffusion effect unique to medium-entropy alloys to significantly slow down the diffusion rate of these elements. Zr element has good biocompatibility and can be infinitely miscible with Ti. Cu element gives the alloy strong antibacterial ability, which reduces the possibility of infection by destroying bacterial cell membranes and inhibiting bacterial growth.

In summary, this patent application aims to provide a preparation method and application of bone-promoting antibacterial titanium alloy, and to provide strong support for technological progress and clinical treatment in the field of bone repair.

Summary of the invention

In view of the problems in the prior art, the present invention provides an osteopromoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, the main purpose of which is to design an antibacterial medium-entropy alloy having both antibacterial functionality and excellent osteopromoting performance.

In order to achieve the above object, the technical solution adopted by the present invention is as follows:

A method for preparing a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material comprises the following steps:

Step 1: Preparation of CoCrMo master alloy

Co, Cr and Mo particles are mixed in proportion to the target alloy component atomic percentage, and smelted twice or more after pretreatment to obtain a stable CoCrMo master alloy, and the CoCrMo master alloy is cut into particles;

Step 2: Preparation of antibacterial master alloy

If the atomic percentage of Cu in the target alloy is greater than 0, Ti and Cu particles are mixed according to the atomic percentage of the target alloy components, smelted twice or more after pretreatment, and cut into antibacterial master alloy particles, which are A alloy particles;

If the atomic percentage of Cu in the target alloy is equal to 0, the Ti particle is the A alloy particle;

Step 3: Preparation of final alloy

The CoCrMo master alloy particles and the A alloy particles are mixed, the Zr particles are placed on the top, and the CoCrMo master alloy particles and the A alloy particles are placed on the bottom. After pretreatment, smelting is performed more than twice to obtain a TiZrCoCrMoCu alloy with bone-promoting and antibacterial functions.

The pretreatment process in steps 1, 2 and 3 is: flushing the raw metal particles with argon gas for multiple times in a vacuum environment; the vacuum degree is 10 ^-4 Pa.

In steps 1 and 2, the purity of all raw metal particles must be above 99.9% (wt.%), the metal particles are ultrasonically cleaned with alcohol to remove oil and dirt, and dried in a fume hood to ensure that there is no foreign matter such as oxide scale on the surface of the metal particles.

In the steps 1, 2 and 3, the raw metal particles are small cylinders with a diameter of 2 mm and a length of 3 mm, wherein the atomic fraction of Cu in the antibacterial master alloy is 40% to 50%.

In the steps 1, 2 and 3, the smelting temperature is 1400-1800° C., the smelting time is 50-65 s, and the smelting is repeated after turning over once.

A bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material is prepared by the method. The general chemical formula of the alloy material is Ti _a Zr _b Co _c Cr _d Mo _e Cu _f (at.%), wherein 33<a≤45, 33<b≤45, 11<c≤15, 5<d≤10, 0.5<e≤2, and 0≤f≤10.

Preferably, the bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material has a compressive strength of 1242-1435 MPa and an elastic modulus of 94-105 GPa; and an antibacterial rate of 95.1% against surface-adherent Escherichia coli.

Preferably, the cell proliferation rate of mouse osteoblasts (MT3T3 cells) co-cultured with the osteogenic TiZrCoCrMoCu antibacterial medium-entropy alloy material after 3, 5, and 7 days is much higher than that of pure Ti, and its surface osteoblast morphology and cell density are also better than those of pure Ti.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention uses vacuum melting technology to adjust the melting power and time according to the atomic fraction of Cu in the antibacterial master alloy, and adds CoCrMo master alloy to complete the preparation of the antibacterial medium entropy alloy through a flip remelting process. The alloy design allows the atomic fractions of elements such as Ti, Zr, Co, Cr, Mo, and Cu to be adjusted within a wide range to achieve the best match between strength, elastic modulus, antibacterial properties and cell compatibility, and is suitable for a variety of application scenarios. Compared with traditional medical implant materials, the preparation process of the present invention is simpler, does not require complex heat treatment, and because it does not contain refractory precious metals such as Nb and Ta, it reduces the melting point of the alloy and improves the casting performance, effectively reducing costs. The alloy combines the excellent biocompatibility and low elastic modulus of titanium alloys with the excellent wear resistance of CoCr alloys. The addition of Cu gives the alloy antibacterial properties, and due to the slow diffusion effect of the medium entropy alloy, the Cu element will slowly diffuse into the surrounding environment of the alloy. This special effect significantly reduces the infection risk of implant surgery without increasing cytotoxicity, thereby promoting wound healing and recovery in patients.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an ARS staining diagram of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Examples 1-3 of the present invention;

FIG2 is an antibacterial flat plate coating diagram of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Examples 1-3 of the present invention;

3 is a significance analysis diagram of the antibacterial rate of the pure Ti sample and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Examples 1-3 of the present invention;

FIG4 is a statistical graph of the 7-day cell proliferation rate of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Examples 1-3 of the present invention;

FIG5 is a fluorescence staining image of the cytoskeleton of pure Ti, Cu samples and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Examples 1-3 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples that do not specify specific conditions are usually based on conventional conditions.

Example 1

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₄₀ Zr ₄₀ Co _12.8 Cr _6.4 Mo _0.8 (at.%), and the addition amount of Ti, Zr, Co, Cr, and Mo single-substance raw materials is calculated according to the chemical formula of the antibacterial medium-entropy alloy. The purity of the single-substance raw materials of Ti, Zr, Co, Cr, and Mo used is above 99% (wt.%). The preparation method comprises the following steps:

Step 1: Preparation of CoCrMo master alloy

The Co, Cr and Mo particles are cleaned, degreased and dried by alcohol ultrasonic cleaning, and the proportions are made according to the atomic percentage of the target alloy components. The weighed Co, Cr and Mo particles are loaded into a water-cooled copper crucible of a magnetic suspension induction melting furnace, and after being evacuated to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800°C and the melting time is 60 seconds. In order to make the composition uniform, the melting is repeated twice to obtain a stable CoCrMo master alloy, and the CoCrMo master alloy is cut into particles;

Step 2: Preparation of final alloy

The CoCrMo master alloy particles and weighed Ti particles were mixed, Zr particles were placed on the top, CoCrMo master alloy particles and Ti alloy particles were placed on the bottom, and loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001 Pa, they were melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature was 1800 ℃ and the melting time was 60 seconds. In order to make the composition uniform, the melting was repeated twice to obtain the osteopromoting TiZrCoCrMo antibacterial medium-entropy alloy material.

Example 2

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₃₈ Zr ₃₈ Co _12.16 Cr _6.08 Mo _0.76 Cu ₅ (at.%), and the addition amount of Ti, Zr, Co, Cr, Mo, and Cu single-substance raw materials is calculated according to the chemical formula of the antibacterial medium-entropy alloy. The purity of the single-substance raw materials of Ti, Zr, Co, Cr, Mo, and Cu used is above 99% (wt.%). The preparation method comprises the following steps:

Step 1: Preparation of CoCrMo master alloy

The Co, Cr and Mo particles are cleaned, degreased and dried by alcohol ultrasonic cleaning, and the proportions are made according to the atomic percentage of the target alloy components. The weighed Co, Cr and Mo particles are loaded into a water-cooled copper crucible placed in a magnetic suspension induction melting furnace, and after being evacuated to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800°C and the melting time is 60 seconds. In order to make the composition uniform, the melting is repeated twice to obtain a stable CoCrMo master alloy, and the CoCrMo master alloy is cut into particles;

Step 2: Preparation of antibacterial master alloy

The weighed Ti particles and Cu particles are loaded into a crucible of a vacuum arc furnace or a vacuum induction furnace in a certain proportion, and the Cu particles are buried in the Ti particles. After evacuation to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800 °C and the melting time is 60 seconds. In order to make the composition uniform, the melting is repeated twice and cut into antibacterial intermediate alloy particles, which are alloy A particles.

Step 3: Preparation of final alloy

The CoCrMo master alloy particles and A alloy particles were mixed, Zr particles were placed on the top, CoCrMo master alloy particles and A alloy particles were placed on the bottom, and loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001Pa, they were melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature was 1800 ℃ and the melting time was 60 seconds. In order to make the composition uniform, the ingot was turned over and melted repeatedly twice to obtain a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy ingot.

Example 3

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₃₆ Zr ₃₆ Co _11.52 Cr _5.76 Mo _0.72 Cu ₁₀ (at.%). According to the chemical formula of the antibacterial medium-entropy alloy, the addition amount of Ti, Zr, Co, Cr, Mo, and Cu single-substance raw materials is calculated. Among them, the purity of the single-substance raw materials of Ti, Zr, Co, Cr, Mo, and Cu used is more than 99% (wt.%). The following steps are included:

Step 1: Preparation of CoCrMo master alloy

The Co, Cr and Mo particles are cleaned, degreased and dried by alcohol ultrasonic cleaning, and the proportions are made according to the atomic percentage of the target alloy components. The weighed Co, Cr and Mo particles are loaded into a water-cooled copper crucible placed in a magnetic suspension induction melting furnace, and after being evacuated to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800°C and the melting time is 60 seconds. In order to make the composition uniform, the melting is repeated twice to obtain a stable CoCrMo master alloy, and the CoCrMo master alloy is cut into particles;

Step 2: Preparation of antibacterial master alloy

The weighed Ti particles and Cu particles are loaded into a crucible of a vacuum arc furnace or a vacuum induction furnace in a certain proportion, and the Cu particles are buried in the Ti particles. After evacuation to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800 °C and the melting time is 60 seconds. In order to make the composition uniform, the melting is repeated twice and cut into antibacterial intermediate alloy particles, which are alloy A particles.

Step 3: Preparation of final alloy

The CoCrMo master alloy particles and A alloy particles were mixed, Zr particles were placed on the top, CoCrMo master alloy particles and A alloy particles were placed on the bottom, and loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001Pa, they were melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature was 1800 ℃ and the melting time was 60 seconds. In order to make the composition uniform, the ingot was turned over and melted repeatedly twice to obtain a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy ingot.

Example 4

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₄₀ Zr ₄₀ Co _12.8 Cr _6.4 Mo _0.8 (at.%), which can also be written as (TiZr) ₈₀ (Co ₆₄ Cr ₃₂ Mo ₄ ) ₂₀ (at.%), wherein Co ₆₄ Cr ₃₂ Mo ₄ is an ASTM F75 alloy that has been widely used in the medical field. According to the chemical formula of the above antibacterial medium-entropy alloy, the addition amount of Ti, Zr, and ASTM F75 alloy raw materials that can be used is calculated. Among them, the purity of the single-substance raw materials of Ti and Zr used reaches 99% (wt.%) or more. The following steps are included:

Step 1: Preparation of CoCrMo master alloy

The ASTM F75 alloy was cut into particles with a diameter of 2 mm and a length of 3 mm, and then cleaned, degreased and dried by alcohol ultrasonic cleaning to obtain a stable CoCrMo master alloy, namely, the ASTM F75 alloy;

Step 2: Preparation of final alloy

CoCrMo master alloy particles and Ti alloy particles are mixed, Zr particles are placed on the top, CoCrMo master alloy particles and Ti alloy particles are placed on the bottom, and loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800 ℃ and the melting time is 60 seconds. In order to make the composition uniform, the ingot needs to be turned over and melted repeatedly twice to obtain a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy ingot. This method avoids the melting of Mo particles and can greatly improve the melting success rate.

Example 5

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₃₈ Zr ₃₈ Co _12.16 Cr _6.08 Mo _0.76 Cu ₅ (at.%), which can also be written as (TiZr) ₇₆ (Co ₆₄ Cr ₃₂ Mo ₄ ) ₁₉ Cu ₅ (at.%), wherein Co ₆₄ Cr ₃₂ Mo ₄ is an ASTM F75 alloy that has been widely used in the medical field. According to the chemical formula of the above antibacterial medium-entropy alloy, the addition amount of Ti, Zr, Cu single substance and ASTM F75 alloy raw material is calculated. The chemical formula of the above antibacterial medium-entropy alloy is used to calculate the preparation of the metallographic alloy of Ti, Zr, and ASTM F75 alloy. Among them, the purity of the single substance raw materials of Ti, Zr, and Cu used reaches 99% (wt.%) or more. The following steps are included:

Step 1: Preparation of CoCrMo master alloy

The ASTM F75 alloy was cut into particles with a diameter of 2 mm and a length of 3 mm, and then cleaned, degreased and dried by alcohol ultrasonic cleaning to obtain a stable CoCrMo master alloy, namely, the ASTM F75 alloy;

Step 2: Preparation of antibacterial master alloy

The weighed Ti particles and Cu particles are loaded into the crucible of a magnetic suspension induction melting furnace or an arc furnace in a certain proportion, and the Cu particles are buried in the Ti particles. After evacuating the air to a vacuum degree of <0.001 Pa, the particles are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800 °C and the melting time is 60 seconds. In order to make the composition uniform, the particles need to be turned over and melted twice, and then cut into antibacterial master alloy particles.

Step 3: Preparation of final alloy

The CoCrMo master alloy particles and the antibacterial master alloy particles are mixed, the Zr particles are placed on the top, and the CoCrMo master alloy particles and the antibacterial master alloy particles are placed on the bottom, and are loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800°C and the melting time is 60 seconds. In order to make the composition uniform, the ingot needs to be turned over and melted repeatedly twice to obtain a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy ingot. This method avoids the melting of Mo particles and can greatly improve the melting success rate.

Example 6

The embodiment of the present invention provides a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy and a preparation method thereof, wherein the general chemical formula is Ti ₃₆ Zr ₃₆ Co _11.52 Cr _5.76 Mo _0.72 Cu ₁₀ (at.%), which can also be written as (TiZr) ₇₂ (Co ₆₄ Cr ₃₂ Mo ₄ ) ₁₈ Cu ₁₀ (at.%), wherein Co ₆₄ Cr ₃₂ Mo ₄ is an ASTM F75 alloy that has been widely used in the medical field. According to the chemical formula of the above antibacterial medium-entropy alloy, the addition amount of Ti, Zr, Cu single substance and ASTM F75 alloy raw material is calculated. The chemical formula of the above antibacterial medium-entropy alloy is used to calculate the preparation of the metallographic alloy of Ti, Zr, and ASTM F75 alloy. Among them, the purity of the single substance raw materials of Ti, Zr, and Cu used reaches 99% (wt.%) or more. The following steps are included:

Step 1: Preparation of CoCrMo master alloy

The ASTM F75 alloy was cut into particles with a diameter of 2 mm and a length of 3 mm, and then cleaned, degreased and dried by alcohol ultrasonic cleaning to obtain a stable CoCrMo master alloy, namely, the ASTM F75 alloy;

Step 2: Preparation of antibacterial master alloy

The weighed Ti particles and Cu particles are loaded into the crucible of a magnetic suspension induction melting furnace or an arc furnace in a certain proportion, and the Cu particles are buried in the Ti particles. After evacuating the air to a vacuum degree of <0.001 Pa, the particles are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800 °C and the melting time is 60 seconds. In order to make the composition uniform, the particles need to be turned over and melted twice, and then cut into antibacterial master alloy particles.

Step 3: Preparation of final alloy

The CoCrMo master alloy particles and the antibacterial master alloy particles are mixed, the Zr particles are placed on the top, and the CoCrMo master alloy particles and the antibacterial master alloy particles are placed on the bottom, and are loaded into a water-cooled copper crucible of a magnetic levitation induction melting furnace. After evacuating the air to a vacuum degree of <0.001 Pa, they are melted under the protection of an argon atmosphere of 1.2 bar. The melting temperature is 1800°C and the melting time is 60 seconds. In order to make the composition uniform, the ingot needs to be turned over and melted repeatedly twice to obtain a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy ingot. This method avoids the melting of Mo particles and can greatly improve the melting success rate.

Figure 1 is an ARS staining image of a pure Ti sample and the bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy prepared in Example 1-3, Figure 2 is an antibacterial flat plate coating image of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium-entropy alloy prepared in Example 1-3; Figure 3 is a bar graph of the antibacterial rate of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium-entropy alloy prepared in Example 1-3 of the present invention; Figure 4 is a statistical graph of the 7-day cell proliferation rate of a pure Ti sample and the TiZrCoCrMoCu antibacterial medium-entropy alloy prepared in Example 1-3; Figure 5 is a cytoskeleton fluorescence staining image of pure Ti, Cu samples and the TiZrCoCrMoCu antibacterial medium-entropy alloy prepared in Example 1-3.

As shown in Figure 1, the density of mineralized nodules on the surface of the TiZrCoCrMoCu antibacterial medium entropy alloys prepared in Examples 1, 2, and 3 is higher than that of pure Ti, and the TiZrCoCrMoCu antibacterial medium entropy alloy prepared in Example 3 has the highest density of mineralized nodules. From these results, it can be inferred that the addition of Cu has a positive effect on promoting cell osteogenesis, especially when the Cu content is high (such as in Example 3). This is of great significance for the development of biomaterials with the ability to promote bone repair and antibacterial properties, indicating that by adjusting the concentration of Cu, the osteogenic properties of the material can be optimized, providing a valuable reference for the design of implant materials.

As shown in Figures 2 and 3, the TiZrCoCrMoCu antibacterial medium-entropy alloys prepared in Examples 1, 2, and 3 all have antibacterial capabilities, and their antibacterial rates are 27.90%, 61.59%, and 95.12%, respectively.

Fig. 4 is a cell proliferation rate diagram, and the cell proliferation rate of the pure Ti sample of the control group is set to 100% as a benchmark. The results show that the cells of the control group show normal proliferation ability, while the cell proliferation rates of the entropy alloy samples (Examples 1, 2, and 3) in the experimental group reach 110.07%, 115.39%, and 120.32%, respectively. These data clearly show that with the increase of Cu content, the cell proliferation rate is also correspondingly improved, proving that the alloy sample promotes cell proliferation and has good biocompatibility. In particular, the alloy in Example 3 shows the highest cell proliferation rate, indicating that Example 3 has both high antibacterial properties and excellent osteogenic ability.

As shown in Figure 5, on the surface of pure Cu, the cells show shrinkage and fragmentation, and the number is relatively small. This phenomenon refers to the strong cytotoxicity of pure Cu to cells, which causes the cells to be unable to grow and reproduce normally. In contrast, the number of cells on the surface of the medium entropy alloy prepared by pure Ti, Examples 1, 2, and 3 is not only more than that on the surface of pure Cu, but also increases compared with pure Ti, especially on the surface of the medium entropy alloy prepared in Example 3, the number of cells is the most abundant, and the cell morphology is full, showing a healthy growth state. This shows that under the appropriate Cu content, the alloy surface not only does not show cytotoxicity, but promotes cell proliferation and healthy growth. Under the condition of precise control of the Cu content, the TiZrCoCrMoCu antibacterial medium entropy alloy can significantly promote the growth of osteoblasts and has excellent antibacterial properties. This discovery is of great significance for the application of alloy materials in the field of biomedical materials, especially in applications where cell growth and tissue regeneration need to be promoted, such as orthopedic implants and oral implants.

Claims (4)

1. A method for preparing a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material, characterized in that the chemical formula of the alloy material is Ti _a Zr _b Co _c Cr _d Mo _e Cu _f , wherein 33<a≤45, 33<b≤45, 11<c≤15, 5<d≤10, 0.5<e≤2, and 0≤f≤10, comprising the following steps: Step 1: Preparation of CoCrMo master alloy Co, Cr and Mo particles are mixed in proportion to the target alloy component atomic percentage, and smelted twice or more after pretreatment to obtain a stable CoCrMo master alloy, and the CoCrMo master alloy is cut into particles; Step 2: Preparation of antibacterial master alloy If the atomic percentage of Cu in the target alloy is greater than 0, Ti and Cu particles are mixed according to the atomic percentage of the target alloy components, smelted twice or more after pretreatment, and cut into antibacterial master alloy particles, which are A alloy particles; If the atomic percentage of Cu in the target alloy is equal to 0, the Ti particle is the A alloy particle; Step 3: Preparation of final alloy The CoCrMo master alloy particles and the A alloy particles are mixed, the Zr particles are placed on the top, and the CoCrMo master alloy particles and the A alloy particles are placed on the bottom, and the pretreatment is followed by smelting for more than two times to obtain a TiZrCoCrMoCu alloy having bone promoting and antibacterial functions; The pretreatment process in steps 1, 2 and 3 is: flushing the raw metal particles with argon gas multiple times in a vacuum environment; the vacuum degree is 10 ^-4 Pa; In the steps 1, 2 and 3, the smelting temperature is 1400-1800° C., the smelting time is 50-65 s, and the smelting is repeated after turning over once. 2. The method for preparing a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material according to claim 1 is characterized in that in steps 1 and 2, the metal particles are ultrasonically cleaned with alcohol to remove oil and then dried in a fume hood. 3. The method for preparing a bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material according to claim 1, characterized in that in steps 1, 2, and 3, the raw metal particles are small cylinders with a diameter of 2 mm and a length of 3 mm. 4. A bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material, prepared by the method according to any one of claims 1 to 3, characterized in that the bone-promoting TiZrCoCrMoCu antibacterial medium-entropy alloy material has a compressive strength of 1242~1435MPa and an elastic modulus of 94~105GPa; and an 8-hour antibacterial rate against Escherichia coli adhered to the surface reaches 95.1%.