Self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy and preparation method

Abstract

The present invention discloses a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy and a preparation method, specifically: preparing a gradient molybdenum-titanium alloy substrate; pre-treating the molybdenum-titanium alloy substrate with a chemical polishing liquid, cleaning and drying, then connecting the negative electrode of a power supply and placing it in a vacuum chamber containing a pure copper product, arc discharge the pure copper into a copper plasma and releasing copper ions, followed by ion implantation, mixing the obtained Ti-Mo-Cu alloy precursor with sulfur powder, performing a sulfurization treatment in an Ar-filled atmosphere, ultrasonic cleaning, and drying to obtain a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy. The Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention is mainly composed of copper ions containing antibacterial properties and a molybdenum-titanium alloy with a nano-molybdenum disulfide structure having photothermal and photocatalytic properties, so that it can quickly and long-lastingly inhibit bacteria while having a self-cleaning effect.

Description

Technical Field

[0001] The invention belongs to the technical field of titanium alloy antibacterial material preparation, and in particular relates to a preparation method of a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy, and also relates to the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy. Background Art

[0002] Titanium alloys are widely used in daily life due to their light weight, high specific strength, and corrosion resistance. For example, in the medical, aerospace, and marine engineering fields, titanium alloys are often made into implants, metal casings, ship hulls, oil pipelines, and more. However, titanium alloys themselves lack antimicrobial properties, and in some complex and closed working environments, they are inevitably subject to biofouling, which in turn affects the original operating environment and is not conducive to normal use and maintenance. Titanium alloys with self-cleaning properties can maintain their surface cleanliness and remove contaminants, reducing maintenance costs and improving equipment reliability, ensuring normal operation in extreme environments. Therefore, the research on self-cleaning titanium alloys that are resistant to microbial fouling is of great demand and significance.

[0003] A Chinese patent application (Application Number: 202311490724.4, Publication Number: CN 117548676 A, Publication Date: 2024-02-13) discloses a low-cost, high-efficiency method for preparing antibacterial copper-titanium alloy sheet materials. The method involves mixing titanium powder and copper powder, then sealing, die-casting, hot-pressing, sintering, and cold-rolling to produce an antibacterial copper-titanium alloy. While this copper-titanium alloy can resist biofouling by releasing copper ions, it lacks self-cleaning properties, which can affect subsequent use. A Chinese patent application (Application Number: 202210944819.8, Publication Number: CN 117568785A, Publication Date: 2024-02-20) discloses a method for preparing a coating. A transition layer of aluminum oxide is first deposited on a titanium alloy substrate using atomic layer deposition. An antibacterial zinc oxide material is then deposited using atomic layer deposition, resulting in the growth of an antibacterial molecular sieve film on the surface of pure titanium or titanium alloy. However, while antimicrobial coatings created through atomic deposition can resist biofouling, they lack self-cleaning properties and exhibit slow antifouling effects. A Chinese patent (Application Number: 202310052559.8, Publication Number: CN 116115836A, Publication Date: May 16, 2023) discloses a surface coating, preparation method, and application for improving the antimicrobial properties of pure titanium or titanium alloy surfaces. The coating, composed of an inner layer, an intermediate transition layer, and an outer layer containing nano-Ag, achieves antimicrobial properties. However, the coating, which resists biofouling by releasing ions, cannot achieve the self-cleaning properties of titanium alloys that allow for reuse. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy, which solves the problem that the existing titanium alloy materials have poor anti-fouling and self-cleaning capabilities.

[0005] Another object of the present invention is to provide a self-cleaning Ti-MoS2-Cu titanium alloy that is resistant to microbial fouling.

[0006] The technical solution adopted by the present invention is a method for preparing a self-cleaning Ti-MoS2-Cu titanium alloy that is resistant to microbial fouling, which is specifically implemented according to the following steps:

[0007] Step 1, preparing a gradient molybdenum-titanium alloy substrate;

[0008] Step 2: pre-treating the molybdenum-titanium alloy substrate in step 1 with a chemical polishing solution, cleaning and drying it, then connecting it to the negative pole of a power supply and placing it in a vacuum chamber containing a pure copper product. Arc discharge is used to convert the pure copper into copper plasma and release copper ions, followed by ion implantation to obtain a Ti-Mo-Cu alloy precursor.

[0009] Step 3: Mix the Ti-Mo-Cu alloy precursor obtained in step 2 with sulfur powder, perform sulfurization treatment in an Ar atmosphere, ultrasonically clean, and dry to obtain a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy.

[0010] The present invention is also characterized in that:

[0011] In step 1, specifically:

[0012] Step 1.1, mixing titanium powder and molybdenum powder with anhydrous ethanol respectively, milling them using a ball mill, and drying them to obtain a molybdenum-titanium mixed powder;

[0013] In step 1.2, a layer of pure titanium powder is first laid and then five layers of molybdenum-titanium mixed powder are stacked, and the molybdenum content in the molybdenum-titanium mixed powder is increased layer by layer. After the powder is fully laid, a die-casting machine is used to perform static die-casting, and then hot-pressed and sintered in an atmosphere containing Ar. After annealing and cooling, a molybdenum-titanium alloy matrix is obtained.

[0014] In step 1.1, the ball-to-material ratio during ball milling is 4:1; the rotation speed is 100-200 rpm; the ball milling time is 20-24 h; and the particle sizes of the molybdenum powder and the titanium powder are both 100 nm-1 μm.

[0015] In step 1.2, the content of the first layer of pure titanium powder accounts for 10% of the total mass of the molybdenum-titanium alloy matrix; the content of the first layer of molybdenum-titanium mixed powder accounts for 12% of the total mass of the molybdenum-titanium alloy matrix; in the first layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1:9; the content of the second layer of molybdenum-titanium mixed powder accounts for 15% of the total mass of the molybdenum-titanium alloy matrix; in the second layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1.5:8.5; the content of the third layer of molybdenum-titanium mixed powder accounts for 18% of the total mass of the molybdenum-titanium alloy matrix; in the third layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2:8; the content of the fourth layer of molybdenum-titanium mixed powder accounts for 21% of the total mass of the molybdenum-titanium alloy matrix; in the fourth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2.5:7.5; the content of the fifth layer of molybdenum-titanium mixed powder accounts for 24% of the total mass of the molybdenum-titanium alloy matrix; in the fifth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 3:7.

[0016] In step 1.2, the static pressing pressure is 180~200 MPa; the holding time is 5~10 min; the sintering temperature is 1800~2000°C; the sintering pressure is 20~40 MPa; the sintering time is 140~180 min; and the annealing temperature is 1550°C.

[0017] In step 2, the chemical polishing solution is composed of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10; during ion injection, the pulse voltage frequency is 10-12 Hz; the pulse voltage duration is 5 s; the pulse voltage is 30-40 kV; the pressure of the vacuum chamber is 5 10 -3 Pa; the ion injection time is 1~3h.

[0018] In step 3, the mass ratio of sulfur powder to molybdenum powder in the molybdenum-titanium alloy is 2:1; the vulcanization temperature is 900-1200° C.; and the vulcanization time is 10-12 hours.

[0019] Another technical solution adopted by the present invention is a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy prepared by a preparation method of the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy.

[0020] The beneficial effects of the present invention are:

[0021] (1) The Ti-MoS2-Cu antimicrobial fouling titanium alloy of the present invention is mainly composed of copper ions with antibacterial properties and a molybdenum-titanium alloy with a photothermal and photocatalytic nanostructure of molybdenum disulfide, which has a self-cleaning effect and can quickly and long-term inhibit bacteria. In addition, the internal MoS2 can use photothermal effects under the excitation of near-infrared light and cooperate with the release of copper ions injected into the alloy to quickly kill bacteria on the alloy surface to achieve the effect of anti-biofouling;

[0022] (2) The Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention can achieve a self-cleaning effect by photocatalytically decomposing dead bacteria adhering to the surface of the alloy under the excitation of near-infrared light. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG1 is a schematic diagram of the internal structure of the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention. DETAILED DESCRIPTION

[0024] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0025] The preparation method of the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention is specifically implemented according to the following steps:

[0026] Step 1, preparing a gradient molybdenum-titanium alloy substrate, specifically:

[0027] Step 1.1, mixing high-purity titanium powder and molybdenum powder with anhydrous ethanol respectively, ball milling using a ball mill, and drying to obtain a molybdenum-titanium mixed powder;

[0028] The ball-to-material ratio during ball milling is 4:1; the rotation speed is 100-200 rpm; and the ball milling time is 20-24 h.

[0029] The particle sizes of molybdenum powder and titanium powder are both 100nm~1μm;

[0030] Step 1.2: First, a layer of pure titanium powder is laid, and then five layers of molybdenum-titanium mixed powder are stacked, and the molybdenum content of the molybdenum-titanium mixed powder is gradually increased. After the powder is fully laid, static die casting is performed using a die casting machine, and then hot pressing and sintering are performed in an atmosphere containing Ar. After annealing and cooling, a molybdenum-titanium alloy matrix is obtained;

[0031] The content of the first layer of pure titanium powder accounts for 10% of the total mass of the molybdenum-titanium alloy matrix;

[0032] The content of the first layer of molybdenum-titanium mixed powder accounts for 12% of the total mass of the molybdenum-titanium alloy matrix; in the first layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1:9;

[0033] The content of the second layer of molybdenum-titanium mixed powder accounts for 15% of the total mass of the molybdenum-titanium alloy matrix; in the second layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1.5:8.5;

[0034] The content of the third layer of molybdenum-titanium mixed powder accounts for 18% of the total mass of the molybdenum-titanium alloy matrix; in the third layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2:8;

[0035] The content of the fourth layer of molybdenum-titanium mixed powder accounts for 21% of the total mass of the molybdenum-titanium alloy matrix; in the fourth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2.5:7.5;

[0036] The content of the fifth layer of molybdenum-titanium mixed powder accounts for 24% of the total mass of the molybdenum-titanium alloy matrix; in the fifth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 3:7;

[0037] Static pressing pressure is 180~200MPa; holding time is 5~10min;

[0038] The sintering temperature is 1800~2000℃; the sintering pressure is 20~40MPa; the sintering time is 140~180min; and the annealing temperature is 1550℃.

[0039] Step 2, preparing a copper ion-doped Ti-Mo-Cu alloy precursor, specifically:

[0040] The molybdenum-titanium alloy substrate in step 1 is pretreated with a chemical polishing solution, cleaned and dried, and then connected to the negative electrode of a power supply and placed in a vacuum chamber containing a pure copper product. The pure copper is converted into copper plasma by arc discharge and copper ions are released, followed by ion implantation to obtain a Ti-Mo-Cu alloy precursor;

[0041] The chemical polishing solution consists of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10;

[0042] During ion implantation, the pulse voltage frequency is 10~12Hz; the pulse voltage duration is 5s; the pulse voltage is 30~40kV; the vacuum chamber pressure is 5 10 -3 Pa; ion injection duration is 1~3h;

[0043] Step 3, preparing a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy, specifically:

[0044] The copper ion-doped Ti-Mo-Cu alloy precursor obtained in step 2 is mixed with sulfur powder,

[0045] The self-cleaning Ti-MoS2-Cu titanium alloy resistant to microbial fouling is obtained by performing sulfurization treatment in an Ar-filled atmosphere, ultrasonic cleaning, and drying.

[0046] The mass ratio of sulfur powder to molybdenum powder in molybdenum-titanium alloy is 2:1; the vulcanization temperature is 900-1200°C; and the vulcanization time is 10-12 hours.

[0047] Figure 1This is a schematic diagram of the internal structure of the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention. It is a reusable anti-fouling titanium alloy prepared by powder metallurgy, ion implantation and combined with sulfurization reaction. It is mainly composed of a molybdenum-titanium alloy with copper ions containing antibacterial properties and a nano-molybdenum disulfide structure with photothermal and photocatalytic properties. The molybdenum-titanium alloy matrix is synthesized by powder metallurgy after mixing molybdenum powder and titanium powder; copper ions are doped into the molybdenum-titanium alloy by ion implantation. The molybdenum disulfide structure can be converted into a molybdenum disulfide structure inside the molybdenum-titanium alloy through the sulfurization process, and finally a titanium alloy with a Ti-MoS2-Cu structure is obtained, which has a self-cleaning effect and can quickly and long-lastingly inhibit bacteria.

[0048] Example 1

[0049] High-purity titanium and molybdenum powders with a particle size of 100 nm were mixed with anhydrous ethanol, and zirconium oxide balls were added at a ball-to-material ratio of 4:1. The mixture was then ball-milled for 20 hours at 100 rpm. After drying, the sample was first layered with pure titanium powder and then five layers of molybdenum-titanium mixed powder, with the molybdenum content of the mixed powder increasing layer by layer. After the mixture was fully layered, a die-casting machine was used at a pressure of 180 MPa for 5 minutes. After casting, the mixture was hot-pressed and sintered at 1800°C for 140 minutes in an atmosphere containing Ar at a pressure of 20 MPa. The molybdenum-titanium alloy matrix was produced after annealing and cooling at 1550°C.

[0050] The content of the first layer of pure titanium powder accounts for 10% of the total mass of the molybdenum-titanium alloy matrix;

[0051] The content of the first layer of molybdenum-titanium mixed powder accounts for 12% of the total mass of the molybdenum-titanium alloy matrix; in the first layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1:9;

[0052] The content of the second layer of molybdenum-titanium mixed powder accounts for 15% of the total mass of the molybdenum-titanium alloy matrix; in the second layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1.5:8.5;

[0053] The content of the third layer of molybdenum-titanium mixed powder accounts for 18% of the total mass of the molybdenum-titanium alloy matrix; in the third layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2:8;

[0054] The content of the fourth layer of molybdenum-titanium mixed powder accounts for 21% of the total mass of the molybdenum-titanium alloy matrix; in the fourth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2.5:7.5;

[0055] The content of the fifth layer of molybdenum-titanium mixed powder accounts for 24% of the total mass of the molybdenum-titanium alloy matrix; in the fifth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 3:7;

[0056] The obtained molybdenum-titanium alloy substrate was pretreated with a chemical polishing solution consisting of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10. After cleaning and drying, it was connected to the negative electrode of a high-voltage power supply and placed on a sample holder. It was then immersed in a gas pressure of 5 10 -3 The copper plasma with positive charge Pa was injected into the vacuum chamber for 1 hour with the parameters of pulse voltage frequency of 10 Hz, pulse voltage duration of 5 s and pulse voltage of 30 kV to prepare Ti-Mo-Cu alloy precursor doped with copper ions.

[0057] A certain amount of sulfur powder was weighed to achieve a mass ratio of 2:1 between sulfur powder and molybdenum powder in the molybdenum-titanium alloy. The prepared precursor sample was then placed in an Ar atmosphere containing sulfur powder and sulfurized at 900°C for 10 hours. Ultrasonic cleaning (using water) was then performed and dried to obtain a self-cleaning Ti-MoS2-Cu titanium alloy resistant to microbial fouling.

[0058] Example 2

[0059] High-purity titanium powder and molybdenum powder with a particle size of 100nm were mixed with anhydrous ethanol respectively, and zirconium oxide balls were added at a ball-to-material ratio of 4:1. The ball mill was used for 20 hours at a rotation speed of 150rpm. After the ground sample was dried, a layer of pure titanium powder was first laid and then five layers of molybdenum-titanium mixed powder were stacked, and the molybdenum content in the molybdenum-titanium mixed powder was increased layer by layer. After it was fully laid, a die-casting machine was used to maintain the pressure for 5 minutes at a pressure of 190MPa. After casting, it was hot-pressed and sintered at 1900℃ for 140min in an atmosphere containing Ar at a pressure of 30MPa, and then annealed and cooled at 1550℃ to obtain a molybdenum-titanium alloy matrix. The obtained molybdenum-titanium alloy matrix was pretreated with a chemical polishing solution composed of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10. After cleaning and drying, it was connected to the negative pole of the high-voltage power supply and placed on the sample holder, and then immersed in a pressure of 5 10 -3 A copper-doped Ti-Mo-Cu alloy precursor was prepared in a vacuum chamber containing positively charged copper plasma (Pa). A pulse voltage of 12 Hz, 5 s, and 35 kV was injected for 3 hours to produce a copper-doped Ti-Mo-Cu alloy precursor. Sulfur powder was weighed to achieve a 2:1 mass ratio of sulfur to molybdenum powder in the molybdenum-titanium alloy. The prepared precursor sample was then placed in an Ar-filled atmosphere containing sulfur powder and sulfurized at 1050°C for 12 hours. The resulting product was then ultrasonically cleaned and dried to produce a self-cleaning Ti-MoS2-Cu titanium alloy resistant to microbial contamination.

[0060] Example 3

[0061] High-purity titanium powder and molybdenum powder with a particle size of 1 μm and a ratio of molybdenum atoms to titanium atoms of 2:8 were mixed with anhydrous ethanol respectively, and zirconium oxide balls were added at a ball-to-material ratio of 4:1. The ball mill was used for 24 hours at a rotation speed of 200 rpm. After the ground sample was dried, a layer of pure titanium powder was first laid and then five layers of molybdenum-titanium mixed powder were stacked, and the molybdenum content in the molybdenum-titanium mixed powder was increased layer by layer. After it was fully laid, a die-casting machine was used to maintain the pressure for 10 minutes at a pressure of 200 MPa. After casting, it was hot-pressed and sintered at 2000°C for 180 minutes in an atmosphere containing Ar at a pressure of 40 MPa, and then annealed and cooled at 1550°C to obtain a molybdenum-titanium alloy matrix. The obtained molybdenum-titanium alloy matrix was pretreated with a chemical polishing solution composed of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10. After cleaning and drying, it was connected to the negative pole of the high-voltage power supply and placed on the sample holder, and then immersed in a pressure of 5 10 -3 Pa is placed in a vacuum chamber in a positively charged copper plasma. A Ti-Mo-Cu alloy precursor doped with copper ions is prepared by continuous injection for 3 hours with the parameters of pulse voltage frequency of 12 Hz; pulse voltage duration of 5 s; and pulse voltage of 40 kV. A certain mass of sulfur powder is weighed so that the mass ratio of sulfur powder to molybdenum powder in the molybdenum-titanium alloy is 2:1. The prepared precursor sample is then placed in an environment containing sulfur powder and filled with Ar atmosphere, sulfurized at 1100 ° C for 12 hours, and then ultrasonically cleaned and dried to obtain a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy.

[0062] Example 4

[0063] High-purity titanium powder and molybdenum powder with a particle size of 1 μm and a ratio of molybdenum atoms to titanium atoms of 2:8 were mixed with anhydrous ethanol respectively, and zirconium oxide balls were added at a ball-to-material ratio of 4:1. The ball mill was used for 20 hours at a rotation speed of 200 rpm. After the ground sample was dried, a layer of pure titanium powder was first laid and then five layers of molybdenum-titanium mixed powder were stacked, and the molybdenum content in the molybdenum-titanium mixed powder was increased layer by layer. After it was fully laid, a die-casting machine was used to maintain the pressure for 5 minutes at a pressure of 200 MPa. After casting, it was hot-pressed and sintered at 2000°C for 140 minutes in an atmosphere containing Ar at a pressure of 40 MPa, and then annealed and cooled at 1550°C to obtain a molybdenum-titanium alloy matrix. The obtained molybdenum-titanium alloy matrix was pretreated with a chemical polishing solution composed of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:10. After cleaning and drying, it was connected to the negative pole of the high-voltage power supply and placed on the sample holder, and then immersed in a pressure of 5 10 -3Pa is placed in a vacuum chamber in a positively charged copper plasma. A Ti-Mo-Cu alloy precursor doped with copper ions is prepared by continuous injection for 1 hour with the parameters of pulse voltage frequency of 12 Hz; pulse voltage duration of 5 s; and pulse voltage of 40 kV. A certain mass of sulfur powder is weighed so that the mass ratio of sulfur powder to molybdenum powder in the molybdenum-titanium alloy is 2:1. The prepared precursor sample is then placed in an environment containing sulfur powder and filled with Ar atmosphere, sulfurized at 1100 ° C for 10 hours, ultrasonically cleaned, and dried to obtain a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy.

[0064] The self-cleaning Ti-MoS2-Cu antimicrobial titanium alloys prepared in Examples 1-4 of the present invention exhibit antibacterial properties through the synergistic effects of copper ion release and photothermal irradiation. The temperature rise results for Examples 1-4, as well as TC4 and the copper-titanium alloy, were shown in Table 1 after 10 minutes of near-infrared light irradiation.

[0065] Table 1 Temperature rise results of Examples 1-4 and the control group under near-infrared light irradiation

[0066]

[0067] To study its antibacterial properties, TC4 and a copper-titanium alloy were co-cultured with Escherichia coli and Staphylococcus aureus for 24 hours in the dark and under near-infrared light, respectively. The antibacterial results are shown in Tables 2 and 3. As can be seen from Tables 2 and 3, the self-cleaning Ti-MoS2-Cu titanium alloy had an inhibition rate of over 90% in both darkness and light conditions, and over 97% after light exposure. In comparison, the self-cleaning Ti-MoS2-Cu titanium alloy prepared by the present invention has a better antibacterial effect.

[0068] Table 2 Antibacterial rate of co-culture of Examples 1-4 and the control group in dark environment

[0069]

[0070] Table 3 Antibacterial rate of co-culture of Examples 1-4 and the control group under light environment

[0071]

[0072] The self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy of the present invention achieves antibacterial properties and a self-cleaning effect through photocatalysis. To this end, Examples 1-4 and the control group were co-cultured with Escherichia coli for 7 consecutive days under light conditions. After each first day of co-culture, the sample was taken out, irradiated with infrared light for 30 minutes, and then continued to co-cultivate on the second day, and this operation was repeated until the 7th day. The antibacterial rate results are shown in Table 4. It can be seen that the antibacterial rate of Examples 1-4 was stably maintained at more than 97% during the 7 days of co-cultivation. This better illustrates that the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy prepared by the present invention has excellent anti-fouling ability and also has excellent self-cleaning effect.

[0073] Table 4 Antibacterial rate of Examples 1-4 and the control group co-cultured for 7 days under light environment

[0074]

Claims

1. A method for preparing a self-cleaning Ti-MoS2-Cu titanium alloy that resists microbial fouling, characterized in that: Please follow the steps below to implement it: Step 1, preparing a gradient molybdenum-titanium alloy substrate; Step 2: pre-treating the molybdenum-titanium alloy substrate in step 1 with a chemical polishing solution, cleaning and drying it, then connecting it to the negative pole of a power supply and placing it in a vacuum chamber containing a pure copper product. Arc discharge is used to convert the pure copper into copper plasma and release copper ions, followed by ion implantation to obtain a Ti-Mo-Cu alloy precursor. The chemical polishing solution is composed of nitric acid, hydrofluoric acid and deionized water in a volume ratio of 4:1:

10. During ion injection, the pulse voltage frequency is 10~12Hz; the pulse voltage duration is 5s; the pulse voltage is 30~40kV; the pressure of the vacuum chamber is 5 10 - 3 Pa; ion injection duration is 1~3h; Step 3: Mix the Ti-Mo-Cu alloy precursor obtained in step 2 with sulfur powder, perform a sulfurization treatment in an Ar atmosphere at a temperature of 900-1200° C. and a sulfurization time of 10-12 hours, perform ultrasonic cleaning, and dry to obtain a self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy.

2. The method for preparing the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy according to claim 1, characterized in that: In the step 1, specifically: Step 1.1, mixing titanium powder and molybdenum powder with anhydrous ethanol respectively, milling them using a ball mill, and drying them to obtain a molybdenum-titanium mixed powder; In step 1.2, a layer of pure titanium powder is first laid and then five layers of molybdenum-titanium mixed powder are stacked, and the molybdenum content in the molybdenum-titanium mixed powder is increased layer by layer. After the powder is fully laid, a die-casting machine is used to perform static die-casting, and then hot-pressed and sintered in an atmosphere containing Ar. After annealing and cooling, a molybdenum-titanium alloy matrix is obtained.

3. The method for preparing the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy according to claim 2, characterized in that: In the step 1.1, the ball-to-material ratio during the ball milling process is 4:1; the rotation speed is 100-200 rpm; the ball milling time is 20-24 hours; and the particle sizes of the molybdenum powder and the titanium powder are both 100 nm-1 μm.

4. The method for preparing the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy according to claim 2, characterized in that: In the step 1.2, the content of the first layer of pure titanium powder accounts for 10% of the total mass of the molybdenum-titanium alloy matrix; the content of the first layer of molybdenum-titanium mixed powder accounts for 12% of the total mass of the molybdenum-titanium alloy matrix; in the first layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1:9; the content of the second layer of molybdenum-titanium mixed powder accounts for 15% of the total mass of the molybdenum-titanium alloy matrix; in the second layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 1.5:8.5; the content of the third layer of molybdenum-titanium mixed powder accounts for 18% of the total mass of the molybdenum-titanium alloy matrix; in the third layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2:8; the content of the fourth layer of molybdenum-titanium mixed powder accounts for 21% of the total mass of the molybdenum-titanium alloy matrix; in the fourth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 2.5:7.5; the content of the fifth layer of molybdenum-titanium mixed powder accounts for 24% of the total mass of the molybdenum-titanium alloy matrix; in the fifth layer of molybdenum-titanium mixed powder, the mass ratio of molybdenum powder to titanium powder is 3:

7.

5. The method for preparing the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy according to claim 2, characterized in that: In the step 1.2, the static pressing pressure is 180-200 MPa; the holding time is 5-10 min; the sintering temperature is 1800-2000° C.; the sintering pressure is 20-40 MPa; the sintering time is 140-180 min; and the annealing temperature is 1550° C.

6. The self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy prepared by the method for preparing the self-cleaning Ti-MoS2-Cu anti-microbial fouling titanium alloy according to any one of claims 1 to 5.

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