Antibacterial titanium alloy article and method of making the same

Abstract

The application discloses an antibacterial titanium alloy product and a preparation method thereof. The preparation method of the antibacterial titanium alloy product comprises the following steps: (1) mixing titanium alloy powder and nanoscale antibacterial active powder to obtain mixed powder; (2) performing forming treatment on the mixed powder to obtain the antibacterial titanium alloy product; wherein the nanoscale antibacterial active powder is nanoscale silver-containing powder or nanoscale copper-containing powder; and the mass ratio of the titanium alloy nanometer powder to the nanoscale antibacterial active powder is (98-99.9):(0.1-2). The method comprehensively considers the influence of the kinetics and thermodynamics process of the dissolution of the antibacterial precipitated phase in the titanium alloy on the content of the antibacterial precipitated phase and the influence of the average interval of the antibacterial precipitated phase on the antibacterial performance. Therefore, the antibacterial effect of the antibacterial titanium alloy product can be significantly improved at a lower nanoscale antibacterial active powder consumption, and the cost of the antibacterial titanium alloy product is effectively reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, in particular, to an antibacterial titanium alloy product and a preparation method thereof, more particularly, to an antibacterial titanium alloy product for daily life, food industry and medical health and a preparation method thereof. BACKGROUND

[0002] With the progress of the level of social and economic development, safety and health issues are getting more and more attention. However, various pathogens existing in the living environment have always been a major hidden danger threatening people's health. Titanium alloy is widely used in biomedical materials, wearable devices and public medical safety fields due to its excellent biocompatibility, high specific strength and good corrosion resistance. However, the existing standard grade pure titanium and its alloys have no obvious antibacterial effect, which brings great safety hazards and health risks to the public. For example, studies have shown that as a biomedical material, pure titanium and its alloys used as implant materials will inevitably cause a certain percentage of patients to be infected by bacteria and produce inflammatory reactions after implantation. Therefore, the development of titanium and titanium alloy with antibacterial properties has great social and economic significance.

[0003] Unlike the common elements in titanium and titanium alloy, metal elements such as silver, copper and zinc naturally have excellent bactericidal function. Unlike traditional bactericides and antibiotics, the antibacterial effect of inorganic metals has the characteristics of broad-spectrum antibacterial, permanent antibacterial, and bacteria will not develop drug resistance. Among them, the antibacterial performance of metal silver and copper is the most outstanding, and they have good biocompatibility, so the biomedical antibacterial titanium alloy with the addition of silver and copper has been widely studied. The main preparation processes include ion implantation, surface coating and alloying. Among them, the method of adding antibacterial metal elements to the substrate through alloying has become one of the hot research directions due to its long-acting antibacterial property and scratch resistance. For example, in the traditional powder metallurgy process, silver powder or copper powder is added to the titanium alloy powder to obtain a mixed powder which is then sintered, and a sufficient amount of silver or copper is added during the casting and smelting of titanium alloy. According to the existing research on bactericidal mechanism and model, the direct contact of silver-rich or copper-rich precipitates in titanium alloy with bacteria plays a very important role in improving antibacterial performance. Only when silver and copper in the titanium alloy matrix exist in the form of silver-rich or copper-rich phase can strong antibacterial effect be produced, and silver or copper in the form of solid solution in the titanium alloy matrix has less contribution to antibacterial ability. However, due to the high solubility of metal silver and copper in the titanium alloy matrix, in order to obtain sufficient silver-rich or copper-rich precipitates to produce antibacterial effect, a relatively high amount of silver or copper is required in the existing alloying process to prepare antibacterial titanium alloy containing silver and copper to produce obvious antibacterial effect. However, this also leads to a high amount of noble metal silver and copper, resulting in high cost of antibacterial titanium alloy, which is not conducive to practical application.

[0004] Therefore, the existing antibacterial titanium alloy product and the preparation method thereof still need to be improved. SUMMARY

[0005] It should be noted that the present application is based on the discovery of the inventors on the following facts and problems:

[0006] On the one hand, the inventors found that, by controlling the kinetics and thermodynamics process of the dissolution of the antibacterial precipitates in the titanium alloy, after uniformly dispersing a small amount of nanoscale antibacterial active powder (such as nanoscale silver-containing powder, nanoscale copper-containing powder, etc.) on the surface of the titanium alloy powder, and then rapidly shaping the composite titanium alloy powder by low-temperature rapid shaping technology, the nanoscale antibacterial active powder can be densified before being solid-solved into the titanium alloy matrix, thereby obtaining a non-equilibrium titanium alloy. The titanium alloy matrix contains sufficient nanoscale antibacterial precipitates, and the average spacing of the nanoscale antibacterial precipitates in the titanium alloy matrix can be adjusted by various common means. Thus, sufficient nanoscale antibacterial precipitates can be obtained in the titanium alloy at a lower dosage of nanoscale antibacterial active powder, so as to obtain excellent antibacterial performance of the antibacterial titanium alloy product. On the other hand, the inventors found that the average spacing of the antibacterial precipitates in the titanium alloy has an influence on the antibacterial performance. By controlling the average spacing of the antibacterial precipitates in the titanium alloy to be comparable to or smaller than the typical size of bacteria, the antibacterial effect of the antibacterial titanium alloy product can be significantly improved. Thus, the antibacterial effect of the antibacterial titanium alloy product can be significantly improved at a lower dosage of nanoscale antibacterial active powder, and the cost thereof can be effectively reduced.

[0007] Therefore, in one aspect of the present application, a method for preparing an antibacterial titanium alloy product is provided. According to an embodiment of the present application, the method comprises: (1) mixing a titanium alloy powder with a nanoscale antibacterial active powder to obtain a mixed powder; (2) performing a shaping treatment on the mixed powder to obtain the antibacterial titanium alloy product; wherein the nanoscale antibacterial active powder is a nanoscale silver-containing powder or a nanoscale copper-containing powder; and the mass ratio of the titanium alloy nanoscale powder to the nanoscale antibacterial active powder is (98-99.9):(0.1-2).

[0008] According to the method for preparing the antibacterial titanium alloy product in the above-mentioned embodiments of the present application, by performing low-temperature rapid forming on the mixed powder of the titanium alloy powder and the nano-scale antibacterial active powder, the nano-scale antibacterial active powder can be densified when it is not in solid solution in the titanium alloy matrix, and a non-equilibrium titanium alloy is obtained. The titanium alloy matrix contains sufficient nano antibacterial precipitates, and the average spacing of the nano antibacterial precipitates in the titanium alloy matrix can be adjusted by various common means. Thus, sufficient nano antibacterial precipitates can be obtained in the titanium alloy at a lower dosage of the nano-scale antibacterial active powder, so that the antibacterial titanium alloy product has excellent antibacterial performance. On the other hand, by adjusting the specific process parameters in the forming process, the average spacing of the antibacterial precipitates in the prepared product can be comparable to or smaller than the typical size of bacteria, so as to further improve the antibacterial effect of the antibacterial titanium alloy, and obtain higher antibacterial performance at a lower dosage of the nano-scale antibacterial active powder.

[0009] In addition, the method for preparing the antibacterial titanium alloy product according to the above-mentioned embodiments of the present application can further have the following additional technical features:

[0010] In some embodiments of the present application, before step (1), the titanium alloy powder is subjected to wet ball milling to obtain a flaky titanium alloy powder, and the flaky titanium alloy powder is used to mix with the nano-scale antibacterial active powder to obtain the mixed powder.

[0011] In some embodiments of the present application, the thickness of the flaky titanium alloy powder is 0.1-5 μm.

[0012] In some embodiments of the present application, in the antibacterial titanium alloy product, the average spacing of the antibacterial precipitates in the titanium alloy matrix is 0.1-5 μm.

[0013] In some embodiments of the present application, the titanium alloy powder comprises at least one of α titanium alloy, (α+β) titanium alloy and β titanium alloy powder.

[0014] In some embodiments of the present application, the titanium alloy powder further comprises pure titanium.

[0015] In some embodiments of the present application, the average particle size of the nano-scale antibacterial active powder is 10-800 nm.

[0016] In some embodiments of the present application, the nano-scale antibacterial active powder is nano silver oxide.

[0017] In some embodiments of the present application, the forming process comprises: performing cold isostatic pressing on the mixed powder to obtain a titanium alloy green part; and performing low-temperature hot extrusion on the titanium alloy green part to obtain the antibacterial titanium alloy product.

[0018] In some embodiments of the present application, the cold isostatic pressing is performed at a pressure of 150-200 MPa and a temperature of 20-40℃.

[0019] In some embodiments of the present application, the low-temperature hot extrusion is performed at a temperature of 450-500℃, an extrusion ratio of (14-18):1, and an extrusion rate of 5-15 mm / s.

[0020] In some embodiments of the present application, the forming process comprises: performing a spark plasma sintering process on the mixed powder to obtain the antibacterial titanium alloy product.

[0021] In some embodiments of the present application, the spark plasma sintering process is performed at a pressure of 40-60 MPa and a temperature of 750-850℃ for 1-10 min.

[0022] In another aspect of the present application, an antibacterial titanium alloy product is provided. According to embodiments of the present application, the antibacterial titanium alloy product is prepared by the method for preparing an antibacterial titanium alloy product of the above embodiments. Thus, the method for preparing the antibacterial titanium alloy product is simple and low in cost, and the antibacterial precipitated phase has a high content, and the average spacing of the antibacterial precipitated phase is comparable to or less than the typical size of bacteria, and the antibacterial performance is better.

[0023] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0024] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings.

[0025] Figure 1 is a distribution diagram of the nano-silver phase in the antibacterial titanium alloy product prepared in Example 1;

[0026] Figure 2 is a comparison diagram of the antibacterial test results of the antibacterial titanium alloy product (a) prepared in Example 1 and standard pure titanium (b). DETAILED DESCRIPTION

[0027] Embodiments of the present application are described in detail below. The embodiments described below are exemplary only and are not intended to limit the present application, which can be embodied in various ways without departing from the spirit thereof. Unless otherwise defined, technical and scientific terms used in the embodiments have the same meaning as those commonly understood by one of ordinary skill in the art to which the present application pertains. Unless otherwise defined, scientific and technical terms used in this disclosure shall have the meanings commonly understood by one of ordinary skill in the art to which this application pertains. The term "antibacterial precipitate phase" and "nanometer antibacterial precipitate phase" can be used interchangeably in this disclosure.

[0028] In one aspect of the present application, a method for preparing an antibacterial titanium alloy product is provided. According to embodiments of the present application, the method comprises: (1) mixing a titanium alloy powder with a nanometer antibacterial active powder to obtain a mixed powder; (2) performing a forming treatment on the mixed powder to obtain an antibacterial titanium alloy product; wherein the nanometer antibacterial active powder is a nanometer silver-containing powder or a nanometer copper-containing powder; and the mass ratio of the titanium alloy nanometer powder to the nanometer antibacterial active powder is (98-99.9):(0.1-2).

[0029] Specifically, in the above mixed powder, the specific mass fraction of the titanium alloy nanometer powder can be 98, 98.1, 98.2, 98.3, 98.4, 98.5, 98.6, 98.7, 98.8, 98.9, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, etc., and the specific mass fraction of the nanometer antibacterial active powder can be 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, etc.

[0030] As described above, the method of the present application can improve the antibacterial performance of the antibacterial titanium alloy by increasing the content of the antibacterial precipitate phase in the antibacterial titanium alloy and controlling the average spacing of the antibacterial precipitate phase in the antibacterial titanium alloy to be comparable to or less than the typical size of bacteria. Two methods that can achieve the above purposes are described below: (I)

[0032] According to some embodiments of the present application, a titanium alloy powder with a fine granularity can be selected, and the average spacing between the nanoparticles is at a suitable value before forming. After mixing with the nanoscale antibacterial active powder, the titanium alloy powder in the composite powder is deformed severely during extrusion by adjusting the extrusion ratio, extrusion temperature and other parameters in the hot extrusion forming process, so that the spacing of the nanoscale antibacterial active powder attached to the surface thereof is further reduced, and the material is rapidly densified. In this way, the product not only has abundant and uniformly distributed antibacterial precipitates inside, but also the average spacing of the antibacterial precipitates meets the requirement of being comparable to or smaller than the typical size of bacteria. (II)

[0034] According to some embodiments of the present application, the titanium alloy powder can be wet ball milled in advance to obtain a lamellar titanium alloy powder. The thickness of the lamellar titanium alloy powder is comparable to or smaller than the typical size of bacteria. In this way, the average spacing of the antibacterial precipitates in the subsequently prepared product meets the required requirement. After mixing with the nanoscale antibacterial active powder, the material is rapidly densified by methods such as hot extrusion and spark plasma sintering (SPS), to obtain a product with abundant and uniformly distributed antibacterial precipitates inside.

[0035] More specifically, the following three methods can be used to achieve the above-mentioned purpose: (I)

[0037] (1) Use a commercially available titanium alloy powder with a suitable size and without wet ball milling, and a nanoscale antibacterial active powder.

[0038] (2) Mix the titanium alloy powder and the nanoscale antibacterial active powder in a predetermined ratio, and uniformly disperse the nanoscale antibacterial active powder on the surface of the titanium alloy powder, to obtain a titanium alloy composite powder with the nanoscale antibacterial active powder uniformly adsorbed on the surface.

[0039] (3) Use cold isostatic pressing to pre-form the composite powder to obtain a green part of the titanium alloy

[0040] (4) After heating the green part obtained in step (3) to a suitable temperature, select a suitable extrusion ratio and mold, and hot extrude the green part to obtain an antibacterial titanium alloy product with a target shape (such as a rod, a pipe, etc.). (II)

[0042] (1) Wet ball mill or other process the titanium alloy powder to obtain a lamellar titanium alloy powder with a predetermined thickness.

[0043] (2) mixing the flaky titanium alloy powder and the nanoscale antibacterial active powder according to a predetermined ratio, and uniformly dispersing the nanoscale antibacterial active powder to the surface of the titanium alloy powder to obtain titanium alloy composite powder having the nanoscale antibacterial active powder uniformly adsorbed on the surface.

[0044] (3) preforming the composite powder by cold isostatic pressing to obtain a green part of the titanium alloy

[0045] (4) heating the green part obtained in step (3) to a suitable temperature, selecting a suitable extrusion ratio and a die, and hot extruding the green part to obtain an antibacterial titanium alloy product (such as a rod or a pipe) of a target shape. (Three)

[0047] (1) wet ball milling or other process treatment is performed on the titanium alloy powder to obtain flaky titanium alloy powder of a predetermined thickness.

[0048] (2) mixing the flaky titanium alloy powder and the nanoscale antibacterial active powder according to a predetermined ratio, and uniformly dispersing the nanoscale antibacterial active powder to the surface of the titanium alloy powder to obtain titanium alloy composite powder having the nanoscale antibacterial active powder uniformly adsorbed on the surface.

[0049] (3) sintering the composite powder obtained in step (2) by spark plasma sintering to obtain an antibacterial titanium alloy product.

[0050] The method for preparing the antibacterial titanium alloy product according to the embodiments of the present application is described in further detail as follows.

[0051] According to some embodiments of the present application, wet ball milling is performed on the titanium alloy powder before the above step (1) to obtain flaky titanium alloy powder, and the flaky titanium alloy powder is used to mix with the nanoscale antibacterial active powder to obtain the mixed powder. The specific method of wet ball milling is not particularly limited and can be the commonly used wet ball milling method in the art. For example, anhydrous ethanol can be used as a process control agent during the wet ball milling process, and a common industrial planetary ball mill can be used.

[0052] According to some embodiments of the present application, the thickness of the above flaky titanium alloy powder is 0.1-5 μm. In this way, the thickness of the flaky titanium alloy powder is comparable to or smaller than the typical size of bacteria. By mixing the flaky titanium alloy powder with the nanoscale antibacterial active powder, the average spacing of the antibacterial precipitated phase in the subsequently prepared product meets the required requirements.

[0053] According to some embodiments of the present application, the average spacing of the antibacterial precipitated phase in the titanium alloy matrix in the antibacterial titanium alloy product is 0.1-5 μm. Thus, the average spacing of the antibacterial precipitated phase meets the requirement of being comparable to, or smaller than, the typical size of bacteria, the performance of the antibacterial precipitated phase is more likely to be exerted, and the performance of the antibacterial titanium alloy product is better.

[0054] In addition, it should be noted that in the present application, the specific source of the titanium alloy powder raw material is not particularly limited, and a commercially available product can be purchased. According to some embodiments of the present application, the titanium alloy powder includes at least one of α titanium alloy, (α+β) titanium alloy, and β titanium alloy powder. In some embodiments of the present application, the titanium alloy powder further includes pure titanium.

[0055] According to some embodiments of the present application, the average particle size of the above-mentioned nanoscale antibacterial active powder is 10-800 nm, for example, 10 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, etc.

[0056] According to some embodiments of the present application, the above-mentioned nanoscale antibacterial active powder is nanoscale silver oxide.

[0057] According to some embodiments of the present application, the above-mentioned forming process includes: performing cold isostatic pressing on the mixed powder of the titanium alloy powder and the nanoscale antibacterial active powder to obtain a titanium alloy green part; and performing low-temperature hot extrusion on the titanium alloy green part to obtain the antibacterial titanium alloy product.

[0058] According to some embodiments of the present application, the cold isostatic pressing is performed at a pressure of 150-200 MPa and a temperature of 20-40℃. Specifically, the cold isostatic pressing pressure can be 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, etc., and the cold isostatic pressing temperature can be 20℃, 25℃, 30℃, 35℃, 40℃, etc. The temperature used in the low-temperature hot extrusion is 450-500℃, the extrusion ratio is (14-18):1, and the extrusion rate is 5-15 mm / s. Specifically, the low-temperature hot extrusion temperature can be 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, etc., the extrusion ratio can be 14:1, 15:1, 16:1, 17:1, 18:1, etc., and the extrusion rate can be 5 mm / s, 7.5 mm / s, 10 mm / s, 12.5 mm / s, 15 mm / s, etc. By performing the cold isostatic pressing and the low-temperature hot extrusion under the above conditions, the nanoscale antibacterial active powder can be further facilitated to realize densification when it is not in solid solution in the titanium alloy matrix, and a non-equilibrium titanium alloy is obtained. Thus, sufficient nanoscale antibacterial precipitates are obtained in the titanium alloy at a lower amount of nanoscale antibacterial active powder, so that the antibacterial titanium alloy product has excellent antibacterial performance. At the same time, the above processing conditions are more conducive to regulating the average spacing of the antibacterial precipitates in the product to meet the requirement that the average spacing of the antibacterial precipitates is comparable to or smaller than the typical size of bacteria. Thus, the antibacterial performance of the product is further improved.

[0059] According to some embodiments of the present application, the forming treatment includes performing a spark plasma sintering treatment on the mixed powder of the titanium alloy powder and the nanoscale antibacterial active powder to obtain the antibacterial titanium alloy product.

[0060] According to some embodiments of the present application, the discharge plasma sintering process described above is performed at a pressure of 40-60 MPa and a temperature of 750-850°C for 1-10 min. Specifically, the processing pressure can be 40 MPa, 45 MPa, 50 MPa, 55 MPa, 60 MPa, etc., the processing temperature can be 750°C, 775°C, 800°C, 825°C, 850°C, etc., and the processing time can be 1 min, 3 min, 5 min, 7 min, 9 min, 10 min, etc. Thus, it can further facilitate the densification of the nanoscale antibacterial active powder when it is not in solid solution in the titanium alloy matrix, so as to obtain a non-equilibrium titanium alloy. Thus, sufficient nanoscale antibacterial precipitates are obtained in the titanium alloy at a lower amount of nanoscale antibacterial active powder, so as to make the antibacterial titanium alloy product have excellent antibacterial performance. At the same time, the above processing conditions are more conducive to regulating the average spacing of the antibacterial precipitates in the product, so as to meet the requirement that the average spacing of the antibacterial precipitates is comparable to or smaller than the typical size of bacteria. Thus, the antibacterial performance of the product is further improved.

[0061] In another aspect of the present application, the present application provides an antibacterial titanium alloy product. According to embodiments of the present application, the antibacterial titanium alloy product is prepared by the method for preparing an antibacterial titanium alloy product described above. Thus, the method for preparing the antibacterial titanium alloy product is simple and low in cost, and the antibacterial titanium alloy product has a high content of antibacterial precipitates, and the average spacing of the antibacterial precipitates is comparable to or smaller than the typical size of bacteria, so as to have better antibacterial performance.

[0062] In addition, it should be noted that all the features and advantages described above for the method for preparing an antibacterial titanium alloy product are also applicable to the antibacterial titanium alloy product, and will not be repeated here.

[0063] The present application will be described below with reference to specific examples, and it should be noted that these examples are merely descriptive and do not limit the present application in any way.

[0064] Example 1

[0065] (1) 99.7 parts by mass of commercial titanium alloy powder (minus 325 mesh) were weighed;

[0066] (2) The titanium alloy powder was wet-milled using an ordinary industrial planetary ball mill with anhydrous ethanol as a process control agent, to obtain lamellar titanium alloy powder;

[0067] (3) 0.3 parts by mass of nano silver oxide is weighed and dispersed in anhydrous ethanol, and then the lamellar powder obtained in step (2) is added to the anhydrous ethanol, and the nano silver oxide is uniformly adsorbed to the surface of the titanium alloy lamellar powder by the adsorption property of the nano particles, and then the anhydrous ethanol is removed to obtain the lamellar titanium alloy composite powder with nano silver oxide adsorbed on the surface;

[0068] (4) The antibacterial titanium alloy sample is obtained by using the spark plasma sintering technology under the pressure of 50 MPa, rapidly heating to 800°C, and furnace cooling after holding for 5 min.

[0069] The distribution of the nano silver phase in the prepared titanium alloy sample is shown in Figure 1

[0070] The titanium alloy sample prepared in Example 1 and the standard pure titanium are taken as samples, and the E. coli culture is observed on the surface of the samples at 37°C for 24 h, and then the washed bacterial liquid is placed on the counting plate for overnight culture, and then the counting and antibacterial rate calculation are carried out. The antibacterial effect of the titanium alloy sample prepared in Example 1 reaches more than 99%. The test results are shown in Figure 2

[0071] Example 2

[0072] (1) 99.6 parts by mass of commercial titanium alloy powder (minus 325 mesh) is weighed;

[0073] (2) The titanium alloy powder is wet milled by using an ordinary industrial planetary ball mill with anhydrous ethanol as a process control agent to obtain lamellar titanium alloy powder;

[0074] (3) 0.4 parts by mass of nano silver oxide is weighed and dispersed in anhydrous ethanol, and then the lamellar powder obtained in step (2) is added to the anhydrous ethanol, and the nano silver oxide is uniformly adsorbed to the surface of the titanium alloy lamellar powder by the adsorption property of the nano particles, and then the anhydrous ethanol is removed to obtain the lamellar titanium alloy composite powder with nano silver oxide adsorbed on the surface;

[0075] (4) The composite powder obtained in step (3) is made into a green body by cold isostatic pressing at a pressure of 180 MPa.

[0076] (5) The hot extrusion die and the green body obtained in step (4) are preheated to 485°C, and the extrusion ratio is controlled to be 16:1 and the extrusion rate is controlled to be 10 mm / s, and the antibacterial titanium alloy bar is obtained by hot extrusion.

[0077] Example 3

[0078] ​​(1) 98 parts by mass of commercial titanium alloy powder (minus 325 mesh) were weighed;

[0079] (2) 2 parts by mass of nano silver oxide were weighed and dispersed in anhydrous ethanol, and then the sheet powder obtained in step (1) was added to the anhydrous ethanol, and the nano silver oxide was uniformly adsorbed to the surface of the titanium alloy powder by the adsorption characteristics of the nano particles, and then the anhydrous ethanol was removed, to obtain titanium alloy composite powder with nano silver oxide adsorbed on the surface;

[0080] (3) The composite powder obtained in step (2) was ball milled for 4 hours under an argon protective atmosphere using a high-energy ball mill, to obtain titanium alloy composite powder with dispersed nano silver oxide particles;

[0081] (4) The ball-milled powder in step (4) was sintered using a spark plasma sintering technique, and under a pressure of 50 MPa, the temperature was rapidly raised to 900°C, and after holding for 5 minutes, the furnace was cooled, to obtain an antibacterial titanium alloy sample.

[0082] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and modified by those skilled in the art without contradiction, within the scope of the present application.

[0083] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. A method of making an antimicrobial titanium alloy article, characterized by, Comprise: (1) mixing a titanium alloy powder with a nano-scale antibacterial active powder to obtain a mixed powder; (2) performing a forming treatment on the mixed powder to obtain the antibacterial titanium alloy product; wherein the nano-scale antibacterial active powder is a nano-scale silver-containing powder or a nano-scale copper-containing powder; the mass ratio of the titanium alloy powder to the nano-scale antibacterial active powder is (98-99.9) : (0.1-2), the forming treatment comprises: performing a cold isostatic pressing treatment on the mixed powder to obtain a titanium alloy green part; performing a low-temperature hot extrusion treatment on the titanium alloy green part to obtain the antibacterial titanium alloy product, the cold isostatic pressing treatment is performed at a pressure of 150-200 MPa and a temperature of 20-40 °C; the low-temperature hot extrusion treatment is performed at a temperature of 450-500 °C, an extrusion ratio of (14-18) : 1, and an extrusion rate of 5-15 mm / s.

2. The method of claim 1, wherein, Before step (1), the titanium alloy powder is subjected to a wet ball milling to obtain a flaky titanium alloy powder, and the flaky titanium alloy powder is used for mixing with the nano-scale antibacterial active powder to obtain the mixed powder.

3. The method of claim 2, wherein, The flaky titanium alloy powder has a thickness of 0.1-5 μm.

4. The method of claim 3, wherein, In the antibacterial titanium alloy product, the average spacing of the antibacterial precipitated phase in the titanium alloy matrix is 0.1-5 μm.

5. The method according to any one of claims 1 to 4, characterized in that, The titanium alloy powder comprises at least one of an α titanium alloy, an (α+β) titanium alloy, and a β titanium alloy powder.

6. The method of claim 5, wherein, The titanium alloy powder further comprises pure titanium.

7. The method of claim 5, wherein, The nano-scale antibacterial active powder has an average particle size of 10-800 nm.

8. The method of claim 1, wherein, The nano-scale antibacterial active powder is nano silver oxide.

9. An antimicrobial titanium alloy article, characterized in that, is prepared by the method of any one of claims 1-8.

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