Preparation Method and Application of an Antibacterial Coating on Titanium Surface

Abstract

The present invention provides a preparation method and application of an antibacterial coating on a titanium surface, belonging to the technical field of metal surface treatment. The preparation method includes: pickling the surface of a titanium material to obtain a pickled titanium material; alkalizing the pickled titanium material in an alkaline solution to form a sodium titanate layer and obtain an alkalized titanium material; vertically placing the alkalized titanium material in a reaction solution containing an iron source and a sulfur source for a hydrothermal reaction to obtain a titanium material with an FeS2 coating; wherein, the iron source in the reaction solution includes any one of ferric chloride, ferrous gluconate, ferrous sulfate, and ferric nitrate, and the sulfur source includes any one of tetraethylthiuram disulfide, thiourea, and thioacetamide. This method prepares a dense-structured FeS2 coating with good bonding force to the pure titanium substrate on the surface of pure titanium by using the vertical solvothermal method, which can improve the antibacterial performance of the pure titanium material and further enhance the biocompatibility of the medical pure titanium material.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal surface treatment, and particularly relates to a preparation method and application of an antibacterial coating on a titanium surface. Background Art

[0002] In the current field of tissue structure restoration and treatment, biomedical metal materials have a series of excellent properties such as high reliability, resistance to fatigue wear, and excellent processing and forming performance, and have been widely used in modern clinical medicine. Currently, the biomedical metal materials used in medical clinical applications mainly include 316L stainless steel, titanium and its alloys, cobalt-based alloys, etc.

[0003] In the field of orthopedic implants, titanium is widely used due to its high strength, corrosion resistance, and biocompatibility. However, titanium materials have inherent deficiencies in antibacterial properties, which may increase the risk of postoperative bacterial colonization and infection. Therefore, improving the antibacterial properties of titanium materials has become an important research direction. Summary of the Invention

[0004] In order to improve the antibacterial properties of pure titanium materials, the present invention provides a preparation method of an antibacterial coating on a titanium surface. This method uses the vertical solvothermal method to prepare a layer of FeS 2 coating on the pure titanium surface, which has a dense structure and good bonding force with the pure titanium substrate, can improve the antibacterial properties of pure titanium materials, and further enhance the biocompatibility of medical pure titanium materials.

[0005] The present invention also provides an application of the preparation method of the antibacterial coating on the titanium surface in the preparation of biomedical materials or medical devices.

[0006] The present invention is achieved through the following technical solutions:

[0007] The present invention provides a preparation method of an antibacterial coating on a titanium surface, and the preparation method includes:

[0008] Pickle the surface of the titanium material to obtain pickled titanium material;

[0009] Place the pickled titanium material in an alkaline solution for alkalization to form a sodium titanate layer and obtain alkalized titanium material;

[0010] Vertically place the alkalized titanium material in a reaction solution containing an iron source and a sulfur source for hydrothermal reaction to obtain titanium material with an FeS 2 coating;

[0011] Wherein, the iron source in the reaction solution includes any one of ferric chloride, ferrous gluconate, ferrous sulfate, and ferric nitrate, and the sulfur source includes any one of tetraethylthiuram disulfide, thiourea, and thioacetamide.

[0012] Further, pickling the titanium material surface to obtain a pickled titanium material, specifically including:

[0013] Pickle the titanium material surface with a mixed acid solution to obtain a pickled titanium material;

[0014] Among them, the mixed acid solution is formed by mixing hydrofluoric acid, nitric acid and water in a volume ratio of 1:4:5.

[0015] Further, placing the pickled titanium material in an alkali solution for alkalization to form a sodium titanate layer and obtain an alkalized titanium material, specifically including:

[0016] Place the pickled titanium material in a 1-10 mol / L sodium hydroxide solution or potassium hydroxide solution for 20-28 h to form a sodium titanate layer and obtain an alkalized titanium material.

[0017] Further, vertically place the alkalized titanium material in a reaction solution containing an iron source and a sulfur source for hydrothermal reaction to obtain a titanium material with an FeS 2 coating, specifically including:

[0018] Vertically place the alkalized titanium material in a reaction solution containing an iron source and a sulfur source, carry out hydrothermal reaction at 140-200 °C for 12-24 h, and obtain a titanium material with an FeS 2 coating.

[0019] Further, in the reaction solution, the concentration of the iron source is 0.03-0.06 mol / L, and the concentration of the sulfur source is 0.04-0.08 mol / L;

[0020] The solvent of the reaction solution includes ethanol.

[0021] Preferably, in the reaction solution, the molar ratio of the iron source to the sulfur source is 1:4.5.

[0022] Preferably, the titanium material includes a pure titanium sheet or a titanium alloy sheet.

[0023] Based on the same inventive concept, the present invention provides a titanium material with an FeS 2 coating, and the titanium material with the FeS 2 coating is prepared by the above method for preparing a titanium surface antibacterial coating.

[0024] Based on the same inventive concept, the present invention provides an application of the method for preparing a titanium surface antibacterial coating in the preparation of biomedical materials or medical devices.

[0025] Based on the same inventive concept, the present invention also provides a titanium material with an FeS 2Application of Coated Titanium Material in the Preparation of Biomedical Materials or Medical Devices

[0026] One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0027] A method for preparing an antibacterial coating on the surface of titanium according to the present invention, which alkalizes the surface of pickled titanium material to form a sodium titanate layer, and then hydrothermally grows FeS on the surface of the alkalized titanium material by the vertical solvothermal method 2 coating, and the FeS obtained by hydrothermal preparation by vertically suspending or placing it on a titanium mesh 2 The coating has a dense structure, can improve the antibacterial performance of pure titanium materials, and further enhance the biocompatibility of medical pure titanium materials. This method is simple to operate, has low energy consumption, and can be prepared in large quantities. Description of the Drawings

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0029] Figure 1 Schematic diagram of the titanium sheet horizontally placed in the inner lining of the reaction kettle in Example 1;

[0030] Figure 2 Schematic diagram of the titanium sheet suspended at a 60° angle to the horizontal plane on the titanium mesh in Example 2;

[0031] Figure 3 Schematic diagram of the titanium sheet suspended at 90° to the horizontal on the titanium wire in Example 3;

[0032] Figure 4 SEM image of the FeS obtained in Example 1 2 coating;

[0033] Figure 5 SEM image of the bacteria morphology on the FeS coating obtained in Example 1 after antibacterial treatment 2 coating;

[0034] Figure 6 SEM image of the FeS coating obtained on the surface of pure titanium in Example 2 of the present invention 2 coating;

[0035] Figure 7 SEM image of the bacteria morphology on the FeS coating obtained in Example 2 after antibacterial treatment 2 coating;

[0036] Figure 8 SEM image of the FeS coating obtained on the surface of pure titanium in Example 3 of the present invention2 SEM image of the coating;

[0037] Figure 9 The FeS obtained in Example 3; 2 Morphology of bacteria on the coating after antibacterial treatment;

[0038] Figure 10 Morphology of bacteria on the titanium surface after antibacterial treatment in Control Example 1;

[0039] Figure 11 From Control Group 1, Example 1, Example 2, Example 3, 2 mM FeS 2 and 2 mM FeSO 4 UV-vis spectra of the catalytic oxidation of ox-TMB. Detailed implementation manners

[0040] The present invention will be specifically described below in combination with the detailed implementation manners and examples, and the advantages and various effects of the present invention will be presented more clearly therefrom. Those skilled in the art should understand that these detailed implementation manners and examples are used to illustrate the present invention, rather than to limit the present invention.

[0041] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as having the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In case of contradiction, this specification shall prevail.

[0042] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in the present invention can be obtained through market purchase or can be prepared by existing methods.

[0043] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0044] The overall idea of the present invention is as follows:

[0045] Mechanical topography antibacterial refers to inhibiting the attachment and growth of bacteria by adjusting the surface morphology and microstructure of materials. The key points include increasing surface roughness to reduce bacterial attachment, using micro-nano structures to interfere with bacterial growth, designing specific shapes to physically damage the bacterial cell wall, combining antibacterial coatings to enhance the effect, and ensuring good biocompatibility to promote cell attachment and inhibit bacteria. By reasonable design and optimization of mechanical topography, the antibacterial performance of materials can be significantly improved and the infection risk can be reduced.

[0046] Iron sulfide Nanoparticles show excellent potential in antibacterial applications, and their peroxidase (POD) activity is usually better than that of traditional iron oxide nanozymes. Its antibacterial mechanism mainly depends on the catalytic generation of hydrogen peroxide The generated reactive free radicals. In addition, as nanozymes with both peroxidase (POD) and catalase (CAT) activities, iron sulfide nanoparticles can efficiently catalyze hydrogen peroxide and promote the release of polysulfide, further enhancing their antibacterial efficiency. This property makes them ideal candidates for developing new and highly efficient antibacterial materials, providing a new technical direction and theoretical support.

[0047] The FeS prepared in the present invention 2 The coating mainly consists of iron and sulfur, and these two elements are both nutrients required by the human body. Therefore, in terms of biosafety, it is more acceptable than other metal sulfides in biological antibacterial treatment. The FeS 2 coating material prepared in the present invention has broad application prospects in the fields of medicine and biotechnology.

[0048] Specifically, a preparation method of an antibacterial coating on a titanium surface according to the present invention includes:

[0049] S1. Pickle the surface of the titanium material to obtain pickled titanium material;

[0050] S2. Alkalize the pickled titanium material in an alkaline solution to form a sodium titanate layer and obtain alkalized titanium material;

[0051] S3. Vertically place the alkalized titanium material in a reaction solution containing an iron source and a sulfur source for hydrothermal reaction to obtain titanium material with an FeS 2 coating;

[0052] Wherein, the iron source in the reaction solution includes any one of ferric chloride, ferrous gluconate, ferrous sulfate and ferric nitrate, and the sulfur source includes any one of tetraethylthiuram disulfide, thiourea and thioacetamide.

[0053] In the present invention, the purpose of pickling the surface of the titanium material is to remove impurities on the titanium surface.

[0054] In the present invention, the purpose of alkalizing the pickled titanium material in an alkaline solution is to form a sodium titanate layer, and the surface morphology of the sodium titanate layer can improve the bonding force between the substrate and FeS 2 . At the same time, a layer of alkaline solution adheres to the surface, so that when immersed in a solution mixed with an iron source and a sulfur source, a thin layer is formed on the surface layer, which is beneficial to the formation of FeS 2 later.

[0055] In the present invention, the alkalized titanium material is placed in a reaction solution containing an iron source and a sulfur source at a certain angle with the horizontal plane for solvothermal reaction. The advantage of placing the titanium sheet non - horizontally is that:

[0056] 1. Uniform deposition: Placing the titanium sheet non - horizontally can reduce the non - uniform deposition of materials on the substrate surface due to gravity. This placement method is beneficial for forming a uniform thin film or coating on the entire substrate because the influence of gravity is relatively uniform in the vertical direction.

[0057] 2. Reducing particle accumulation: When the titanium sheet is placed non - horizontally, the deposited particles are not easily accumulated on the substrate surface, thus reducing the mutual occlusion between particles and promoting more uniform growth.

[0058] 3. Optimizing solution flow: The substrate with the non - horizontally placed titanium sheet is beneficial for the natural convection and flow of the solution, ensuring that the reactants flow uniformly through the substrate surface. This flow can promote the uniform growth of materials and improve the quality of materials.

[0059] 4. Space utilization efficiency: Placing the titanium sheet non - horizontally can more effectively utilize the space in the reaction kettle, allowing multiple substrates to be processed simultaneously in one reaction kettle, thus improving production efficiency.

[0060] In the present invention, the coating plays an antibacterial role. The principle is that compared with the flat surface, the significantly improved bactericidal efficiency on the surface of the nanosheet network structure is mainly attributed to the larger total contact adhesion area. This increased surface area can enhance the tensile strain of the cell membrane, which will cause cell lysis when reaching a certain degree, thus realizing mechanical sterilization. The mechanical sterilization mechanism exerts pressure on bacteria through the physical structure, ultimately leading to the rupture of the bacterial cell membrane and cell death. This method does not rely on chemical agents, so it is expected to slow down the development of drug resistance and provide a lasting effect in various antibacterial applications. At the same time, ferrous ions in can catalyze hydrogen peroxide to generate hydroxyl radicals in specific conditions. This process is called the Fenton reaction. Hydroxyl radicals are strong oxidants that can effectively destroy the cell wall, membrane structure and internal biomolecules of bacteria, thus realizing antibacterial effects.

[0061] In the present invention, the sulfur source is tetraethylthiuram disulfide. Compared with other sulfurizing agents, the by - products generated by the decomposition of tetraethylthiuram disulfide are relatively simple, reducing the possibility of impurity introduction, thereby improving the purity of the product.

[0062] After alkalizing the titanium sheet in the present invention, the presence of a layer of sodium titanate is formed on the surface, and a network structure will be formed during the hydrothermal process, promoting the adhesion of iron sulfide on the titanium surface. After alkalizing the titanium sheet, directly put the titanium sheet into the reaction kettle for reaction. At this time, the residual sodium hydroxide will react with the iron source in the solution to generate , enriching the iron source on the surface. When placed horizontally, spherical FeS will be formed on the surface2 , which is due to the formation of FeS in the solution 2 falling on the titanium surface. Subsequently, when the titanium sheet is not placed horizontally, sulfidation will cause a dense layer structure of iron sulfide flakes to appear.

[0063] Among them, step S1 specifically includes:

[0064] Pickle the surface of the titanium material with a mixed acid solution to obtain pickled titanium material;

[0065] Among them, the mixed acid solution is formed by mixing hydrofluoric acid, nitric acid and water in a volume ratio of 1:4:5.

[0066] Step S2 specifically includes:

[0067] Place the pickled titanium material in a sodium hydroxide solution or potassium hydroxide solution with a concentration of 1-10 mol / L and alkalize it for 20-28 h to form a sodium titanate layer and obtain alkalized titanium material.

[0068] Step S3 specifically includes:

[0069] Vertically place the alkalized titanium material in a reaction solution containing an iron source and a sulfur source, carry out a hydrothermal reaction at 140-200 °C, and the reaction time is 12-24 h to obtain titanium material with an FeS 2 coating.

[0070] In the present invention, the hydrothermal reaction temperature is 140-200 °C. Tetraethylthiuram disulfide releases sulfur by decomposition under solvothermal conditions. Too high a temperature will damage the inner lining of the reaction kettle, and too low a temperature will cause tetraethylthiuram disulfide to fail to release sulfur at a sufficient temperature.

[0071] In the reaction solution, the concentration of the iron source is 0.03-0.06 mol / L, and the concentration of the sulfur source is 0.04-0.08 mol / L;

[0072] The solvent of the reaction solution includes ethanol.

[0073] Preferably, in the reaction solution, the molar ratio of the iron source to the sulfur source is 1:4.5.

[0074] In the present invention, the advantage of the molar ratio of the iron source to the sulfur source being 1:4.5 is that it can ensure that the iron source reacts completely.

[0075] Next, the preparation method and application of an antibacterial coating on titanium surface of the present invention will be described in detail in combination with examples and experimental data.

[0076] The technical solution of the present invention mainly includes two major steps: one is equipment pretreatment; the other is preparation process. Equipment pretreatment mainly includes:

[0077] Pretreatment of the polytetrafluoroethylene-lined reactor and titanium wire and titanium mesh: Before the hydrothermal reaction, the titanium wire or titanium mesh is put into the lining of the polytetrafluoroethylene-lined reactor, and then 30 mL of ultrapure water and 15 mL of 66 - 68% nitric acid are added into the lining. The reactor is tightened and then cleaned under the condition of 140 °C for 8 h.

[0078] Example 1

[0079] A preparation method of an antibacterial coating on titanium surface in this example specifically includes:

[0080] (1) Cut the TA2 pure titanium sheet into a size of 0.3×10×10 mm, and pickle the surface of the TA2 pure titanium sheet with a mixed acid solution to obtain pickled titanium material. The mixed acid solution is formed by mixing hydrofluoric acid, nitric acid and water according to a volume ratio of 1:4:5;

[0081] (2) Place the pickled TA2 pure titanium sheet in a 5 mol / L sodium hydroxide solution and alkalize it for 24 h to form a sodium titanate layer and obtain alkalized titanium material;

[0082] (3) Horizontally place the alkalized titanium material in a polytetrafluoroethylene-lined reactor as shown in Figure 1 and then pour 40 ml of an ethanol solution containing 0.488 g of and 0.712 g of tetraethylthiuram disulfide into the polytetrafluoroethylene lining, fasten the reactor, and place it in a blast drying oven at 200 °C for reaction. After 12 h, take it out to obtain a titanium sheet with a coating on its surface. The SEM of the obtained coating structure is as shown in Figure 4 .

[0083] In the present invention, when the iron source and the sulfur source tetraethylthiuram disulfide are ultrasonically treated and dissolved in ethanol, they can be dissolved more uniformly.

[0084] Example 2

[0085] A preparation method of an antibacterial coating on titanium surface in this example specifically includes:

[0086] (1) Pickle the surface of the TA2 pure titanium sheet with a mixed acid solution to obtain pickled titanium material. The mixed acid solution is formed by mixing hydrofluoric acid, nitric acid and water according to a volume ratio of 1:4:5;

[0087] (2) Place the pickled TA2 pure titanium sheet in a 5 mol / L sodium hydroxide solution and alkalize it for 24 h to form a sodium titanate layer and obtain alkalized titanium material;

[0088] (3) Vertically place the alkalized titanium material in, for example, Figure 2 a titanium mesh. Then pour 40 mL of an ethanol solution containing 0.488 g of and 0.712 g of tetraethylthiuram disulfide into a polytetrafluoroethylene-lined reaction kettle. Subsequently, immerse the titanium mesh with the alkalized titanium material into this solution; tighten the reaction kettle and place it in a forced-air drying oven at 200 °C for reaction. After 12 h, take it out to obtain a titanium sheet with a coating on its surface. The SEM of the obtained coating structure is as shown in Figure 6 shown.

[0089] Example 3

[0090] A method for preparing an antibacterial coating on titanium surface in this example specifically includes:

[0091] (1) Pickle the surface of a TA2 pure titanium sheet with a mixed acid solution to obtain a pickled titanium material. The mixed acid solution is prepared by mixing hydrofluoric acid, nitric acid, and water in a volume ratio of 1:4:5;

[0092] (2) Place the pickled TA2 pure titanium sheet in a 5 mol / L sodium hydroxide solution and alkalize it for 24 h to form a sodium titanate layer and obtain an alkalized titanium material;

[0093] (3) Vertically suspend the alkalized titanium material with titanium wire or iron wire (as shown in Figure 3 ) in the reaction kettle. Pour 40 mL of an ethanol solution containing 0.488 g of and 0.712 g of tetraethylthiuram disulfide into the polytetrafluoroethylene lining, tighten the reaction kettle, and place it in a forced-air drying oven at 200 °C for reaction. After 12 h, take it out to obtain a titanium sheet with a coating on its surface. The SEM of the obtained coating structure is as shown in Figure 8 shown.

[0094] Comparative Example 1

[0095] In this example, a preferred TA2 pure titanium sheet is used as the substrate, and pickling is carried out with a mixed acid solution to remove surface oxides. The mixed acid solution is prepared by mixing hydrofluoric acid, nitric acid, and water in a volume ratio of 1:4:5.

[0096] Test Example 1

[0097] Use 100 µL of a solution with a concentration of 10 6E. coli solutions with CFU / mL were used to inoculate the samples prepared in Examples 1-3 and Comparative Example 1 respectively. After inoculation, the samples were placed in a bacterial incubator for 4 hours. Subsequently, 900 μL of normal saline was used to elute the surface of each sample. After elution, the eluted liquid was aspirated and transferred to a centrifuge tube. Then, 10 μL of the liquid was taken for plating respectively, and 10 μL of the liquid was taken from the centrifuge tube, diluted 100 times and then plated. All the plated culture dishes were placed in a bacterial incubator at 37°C for 18 hours. The antibacterial effect was calculated by the plate counting method.

[0098] The antibacterial efficiency of the sample was calculated using the following formula:

[0099] Antibacterial efficiency

[0100] Among them, A represents the number of colonies corresponding to the sample of Comparative Example 1, and B represents the number of colonies corresponding to the sample of the experimental group.

[0101] Table 1 Antibacterial performance test of the coating

[0102]

[0103] From the antibacterial performance test, it can be seen that the titanium sheets with FeS 2 coatings have excellent antibacterial effects, and their antibacterial effects are all above 95%. Among them, the antibacterial effect of Example 3 is the best. As Figure 6 shown, this may be because a more uniform and dense structure was formed in Example 2.

[0104] Test Example 2

[0105] The method of bacterial inoculation and culture was as described in Test Example 1. The difference was that after culturing, 900 μL of 2.5% glutaraldehyde was added for bacterial fixation, and the fixation time was overnight. The next day, the fixed bacteria were dried successively with 30%, 50%, 70%, 90%, 100% and 100% absolute ethanol. The interval was 10 min each time.

[0106] As Figure 10 shown, the cell membrane of E. coli on the titanium substrate was in a complete state, indicating that the bacterial structure was not damaged. The titanium substrate had no antibacterial effect on E. coli, which was consistent with Table 1. As Figure 5 、 7 and 9 shown, the cytoplasm of bacteria flowed out on the surface of the samples with coatings, and the bacteria were elongated. The coatings had antibacterial effects, which were consistent with the results in Table 1.

[0107] Test Example 3

[0108] 3,3,5,5 - Tetramethylbenzidine (TMB) is commonly used as a molecular probe to detect peroxidase - like properties. It can be oxidized to blue - colored oxidized TMB in the presence of hydroxyl groups and has a characteristic absorption peak at 652 nm. Mix TMB, H 2 O 2 with samples (Control Example 1, Example 1, Example 2, Example 3, 2 mM FeS 2 and 2 mM FeSO 4 ) and incubate the mixture at 37 °C for 30 minutes. The color of the mixed solution changed significantly, turning dark blue. The purpose of testing FeSO 4 is to use FeSO 4 as a positive control group. The purpose of testing FeS 2 is to illustrate that FeS 2 powder also has the Fenton effect of catalyzing hydrogen peroxide to generate hydroxyl radicals.

[0109] As Figure 11 shown in the small figure, the color of the control group did not change, while the color of different example groups turned blue. According to Figure 11 the test results of UV - vis spectroscopy, all example groups had peaks at 652 nm, indicating that the example groups all had the ability to catalyze hydrogen peroxide to generate hydroxyl radicals. According to the test results of 2 mM FeS 2 , their ability to catalyze hydrogen peroxide to generate hydroxyl radicals can be attributed to FeS 2 . 4 Finally, it should also be noted that the term "comprising", "including" or any other variant thereof is intended to cover non - exclusive inclusion, such that a process, method, article or device comprising a series of elements not only includes those elements but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or device.

[0110] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications once they know the basic creative concept. Therefore, the appended claims are intended to be construed to include the preferred embodiments as well as all changes and modifications falling within the scope of the present invention.

[0111] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. A method for preparing an antibacterial coating on a titanium surface, characterized in that: The preparation method comprises: Pickling the surface of the titanium material to obtain the pickled titanium material; placing the acid-washed titanium material in a 1-10 mol / L sodium hydroxide solution for alkalization for 20-28 hours to form a sodium titanate layer, thereby obtaining an alkalized titanium material; The alkalized titanium material is vertically placed in a reaction solution containing an iron source and a sulfur source to perform a hydrothermal reaction to obtain a titanium material containing a FeS2 coating; Wherein, the iron source in the reaction solution includes any one of ferric chloride, ferrous gluconate, ferrous sulfate and ferric nitrate, and the sulfur source includes any one of tetraethylthiuram disulfide, thiourea and thioacetamide.

2. The method for preparing an antibacterial coating on a titanium surface according to claim 1, characterized in that: The pickling of the titanium material surface to obtain the pickled titanium material specifically includes: A mixed acid solution is used to pickle the surface of the titanium material to obtain a pickled titanium material; The mixed acid solution is prepared by mixing hydrofluoric acid, nitric acid and water in a volume ratio of 1:4:

5.

3. The method for preparing an antibacterial coating on a titanium surface according to claim 1, characterized in that: The alkalized titanium material is vertically placed in a reaction solution containing an iron source and a sulfur source to perform a hydrothermal reaction to obtain a titanium material containing a FeS2 coating, which specifically includes: The alkalized titanium material is vertically placed in a reaction solution containing an iron source and a sulfur source, and a hydrothermal reaction is carried out at 140 to 200° C. The reaction time is 12 to 24 hours to obtain a titanium material containing a FeS2 coating.

4. The method for preparing an antibacterial coating on a titanium surface according to claim 1, characterized in that: In the reaction solution, the concentration of the iron source is 0.03-0.06 mol / L, and the concentration of the sulfur source is 0.04-0.08 mol / L; The solvent of the reaction solution includes ethanol.

5. The method for preparing an antibacterial coating on a titanium surface according to claim 1, characterized in that: The titanium material includes a pure titanium sheet or a titanium alloy sheet.

6. A titanium material containing FeS2 coating, characterized in that: The titanium material containing the FeS2 coating is prepared by the method for preparing an antibacterial coating on a titanium surface according to any one of claims 1 to 5.

7. Use of the method for preparing an antibacterial coating on a titanium surface as claimed in any one of claims 1 to 5 in preparing biomedical materials or medical devices.

8. Use of the titanium material containing FeS2 coating as claimed in claim 6 in the preparation of biomedical materials or medical devices.

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