CN117568658A

CN117568658A - High-strength antibacterial titanium alloy material for additive manufacturing and preparation method and application thereof

Info

Publication number: CN117568658A
Application number: CN202311591509.3A
Authority: CN
Inventors: 常成; 闫星辰; 董东东; 高硕洪; 刘敏; 褚清坤
Original assignee: Institute of New Materials of Guangdong Academy of Sciences
Current assignee: Institute of New Materials of Guangdong Academy of Sciences
Priority date: 2023-11-27
Filing date: 2023-11-27
Publication date: 2024-02-20

Abstract

The invention provides a high-strength antibacterial titanium alloy material for additive manufacturing, and a preparation method and application thereof, wherein the high-strength antibacterial titanium alloy material for additive manufacturing comprises the following element components in percentage by mass: mo:8.51 to 15.45 percent; zr:4.2 to 8.2 percent; fe:1.1 to 6.2 percent; cu:2.0 to 6.1 percent; the balance being Ti and unavoidable impurities; c in the impurities is less than or equal to 0.08%; n is less than or equal to 0.05%; h is less than or equal to 0.015 percent; o is less than or equal to 0.20 percent. The material has the advantages that the elastic modulus of the titanium alloy material is effectively reduced, the hardness is high, the impurities are few, the alloy purity is high, the oxygen content can be controlled below 1000ppm, the welding property and the formability are good, meanwhile, the biocompatibility is excellent, the bacterial infection resistance of the material is enhanced, the bioactivity can be promoted, the traditional titanium alloy is converted into the bioactive material from the bioactive material, the material is suitable for various additive manufacturing technologies such as selective laser melting and selective laser sintering as a medical material, and the material application range in the additive manufacturing field is enlarged.

Description

High-strength antibacterial titanium alloy material for additive manufacturing and preparation method and application thereof

Technical Field

The invention relates to the technical field of metal materials, in particular to a high-strength antibacterial titanium alloy material for additive manufacturing, and a preparation method and application thereof.

Background

Titanium (Ti) is one of the most widely used metallic materials for oral medical use at present. However, the elastic modulus (about 110 GPa) of conventional titanium and titanium alloy is far higher than that of human bone (about 30 GPa), and stress shielding is often generated due to the excessively high elastic modulus, so that shearing force/compressive stress applied to surrounding bone tissue is shielded, and the bone tissue is not sufficiently bearing pressure and absorbed and atrophy, so that problems of bone density reduction, bone mass reduction and the like are caused; titanium is a biological inert material, does not have biological activities such as antibacterial and the like, and often causes infection due to bacteria adhesion in an open microbial environment (such as oral cavity and bone defect part of a human body), such as peri-implant inflammation, tooth enamel demineralization and gingivitis after orthodontic treatment, infection after joint replacement surgery and the like. The data of the handbook for prevention and treatment of nosocomial infections issued by the world health organization shows that there are more than 1400 ten thousand nosocomial infected patients worldwide, about 60% of which are associated with implant infections.

In recent years, copper (Cu), titanium and titanium alloy composite materials have attracted extensive attention in research and engineering circles, on the one hand, cu is a good beta-Ti phase stabilizing element in a titanium alloy system, and is beneficial to promoting the further reduction of elastic modulus; on the other hand, cu is a trace element necessary for human body, has good biocompatibility, can catalyze the synthesis of hemoglobin, participates in the development of a cardiovascular system and the like, and simultaneously, cu formed by Cu alloying ²⁺ The ions have strong bactericidal effect and can effectively strengthen the alloyThe ability of the material to resist bacterial infection.

Chinese patent CN102212717A, a copper-containing antibacterial titanium alloy and a preparation method thereof, and CN102936670A, an anti-infective medical titanium alloy, both mention that adding a certain amount of Cu element into the titanium alloy can promote bioactivity and improve antibacterial performance, but the influence of the addition of Cu element on different types of titanium alloys, especially the influence on the mechanical properties thereof, is not considered in the above patent; the preparation methods of the Cu-containing antibacterial titanium alloy are provided in the patents of CN102943190A 'anti-infection medical titanium alloy' and CN108454190A 'an antibacterial titanium alloy composite plate and a preparation method thereof', but the preparation methods have the advantages that the preparation methods need to be subjected to multi-step pretreatment such as hot rolling, forging or vacuum hot pressing, and the like, and then the material can be obtained by machining through multiple heat treatments, so that the steps are complicated, obvious element segregation exists in the material, and the prepared antibacterial titanium alloy has low tissue uniformity and poor stability.

Compared with the traditional manufacturing or machining technology, the additive manufacturing technology can be used for rapidly forming a plurality of metal materials with different melting points, and the forming process does not need auxiliary work such as a die, a cutter and the like, so that the alloy material with complex shape and excellent comprehensive mechanical property can be formed at one time. And the forming material has a fast solidification unbalanced structure with no macrosegregation and compact structure of components, and has excellent comprehensive mechanical properties.

Chinese patent CN115301940B discloses Ti-Zr-Cu titanium alloy powder for laser additive manufacturing, a preparation method and application thereof, but the Ti-Zr-Cu titanium alloy powder has too high Cu content and can play a certain role in inhibiting cells, so that the alloy material obtained by the titanium alloy powder has poor biocompatibility.

Therefore, the development of the high-strength antibacterial titanium alloy material for additive manufacturing, which is applicable to 3D printing and has low modulus, antibacterial property and high biocompatibility, and the preparation method thereof have great significance.

Disclosure of Invention

In view of the problems of over high elastic modulus, complex preparation and poor biocompatibility of the existing titanium alloy medical material, the invention provides a high-strength antibacterial titanium alloy material for additive manufacturing, which is suitable for various additive manufacturing technologies such as selective laser melting, selective laser sintering and the like, has proper elastic modulus, high biocompatibility, can promote bioactivity and has excellent antibacterial performance.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

the high-strength antibacterial titanium alloy material for additive manufacturing comprises the following element components in percentage by mass:

mo:8.51 to 15.45 percent; zr:4.2 to 8.2 percent; fe:1.1 to 6.2 percent; cu:2.0 to 6.1 percent; the balance being Ti and unavoidable impurities;

c in the impurities is less than or equal to 0.08%; n is less than or equal to 0.05%; h is less than or equal to 0.015 percent; o is less than or equal to 0.20 percent.

The invention further aims to provide a preparation method of the high-strength antibacterial titanium alloy material for additive manufacturing.

The preparation method of the high-strength antibacterial titanium alloy material for additive manufacturing comprises the following steps of:

s1, weighing high-purity ingots of ZrFe, moFe and Ti according to mass percentages, smelting, cooling and forging to obtain bars;

s2, carrying out vacuum gas atomization on the bar stock obtained in the S1 to prepare powder, wherein the atomization powder blowing pressure is 0.3-1.2 MPa, and obtaining Ti-Mo-Zr-Fe alloy powder;

s3, ball-milling the Ti-Mo-Zr-Fe alloy powder obtained in the S2 and pure copper powder, and vacuum drying to obtain Ti-Mo-Zr-Fe-xCu powder, thereby obtaining the high-strength antibacterial titanium alloy material for additive manufacturing.

Further, the purity of the high-purity ingots of ZrFe, moFe and Ti in S1 is more than or equal to 99.90 wt%.

Further, the purity of the pure copper powder of S3 is more than or equal to 99.90 wt%.

Further, the vacuum gas atomization in S2 is performed under the protection of argon, and the temperature is 1800-2000 ℃.

Further, the grain size of the Ti-Mo-Zr-Fe alloy powder in S3 is 35-65 mu m, and the grain size of the pure copper powder is 200 nm-10 mu m.

And the ball milling powder mixture is carried out under the protection of argon for 1-2 hours, the rotating speed is 150-250 r/min, and the ball mass ratio is (3-5): 1.

Further, the vacuum drying temperature of S3 is 80-150 ℃ and the pressure is-0.8-0.1 bar.

The invention further aims to provide an application of the high-strength antibacterial titanium alloy material for additive manufacturing.

A high-strength antimicrobial titanium alloy material for additive manufacturing according to any one of the preceding claims for laser 3D printing.

Compared with the prior art, the invention has the following advantages:

(1) According to the high-strength antibacterial titanium alloy material for additive manufacturing, the elastic modulus of the titanium alloy is greatly reduced through the addition of Cu, and the proportion of Cu element is strictly regulated, so that on one hand, proliferation and differentiation of MC3T3-E1 osteoblast precursor cells are greatly promoted, the traditional titanium alloy is changed into a bioactive material from a biological inert material, and on the other hand, the antibacterial effect of the Ti-Mo-Zr-Fe-xCu alloy material on staphylococcus aureus is promoted to different degrees, so that the high-strength antibacterial titanium alloy material for additive manufacturing has high biocompatibility, can promote bioactivity and has excellent antibacterial performance.

(2) The high-strength antibacterial titanium alloy material for additive manufacturing is prepared by firstly smelting intermediate alloy with similar melting points to prepare required bar stock, then vacuum gas atomization to prepare Ti-Mo-Zr-Fe powder, ball-milling and mixing the Ti-Mo-Zr-Fe-xCu powder with pure Cu particles to prepare Ti-Mo-Zr-Fe-xCu powder, controlling the element to be uniformly melted, reducing the influence caused by element segregation, and the obtained powder has good sphericity, high stability, few satellite balls and uniform particle size distribution range; the Ti-Mo-Zr-Fe-xCu alloy material obtained by 3D printing of the Ti-Mo-Zr-Fe-xCu powder mainly comprises equiaxed crystal, and the phases mainly comprise beta-Ti and Ti-Cu phases, so that the hardness of the alloy material is improved, the impurities are less, the alloy purity is high, the oxygen content can be controlled below 1000ppm, and the welding property and the formability are good.

(3) The high-strength antibacterial titanium alloy material for additive manufacturing disclosed by the invention is used for processing a mixed material with a specific proportion by utilizing the advantage of additive manufacturing, endows the traditional titanium-based material with antibacterial property, has proper elastic modulus and high biocompatibility, can promote bioactivity, has excellent antibacterial property, is suitable for various additive manufacturing technologies such as selective laser melting, selective laser sintering and the like, and expands the use scope of materials in the field of additive manufacturing.

Drawings

The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.

Fig. 1 is a microstructure morphology of a sample obtained by additive manufacturing of the high-strength antibacterial titanium alloy material for additive manufacturing of example 1.

FIG. 2 is a microstructure morphology of the Ti-Mo-Zr-Fe alloy powders prepared in comparative example 5.

FIG. 3 is a microstructure morphology of the Ti-Mo-Zr-Fe alloy powders prepared in comparative example 6.

Fig. 4 is a microstructure morphology of the high-strength antibacterial titanium alloy material for additive manufacturing prepared in comparative example 7.

Fig. 5 is a graph of CT morphology of the porous structure made according to the present invention taken out after implantation into a rat body for 12 weeks.

Detailed Description

For a better illustration of the objects, technical solutions and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following embodiments are only some, but not all, embodiments of the invention; it should be understood that the embodiments of the present invention are only used for illustrating the technical effects of the present invention, and are not used for limiting the scope of the present invention.

The starting materials in the examples are all commercially available; unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.

Example 1

A preparation method of a high-strength antibacterial titanium alloy material for additive manufacturing comprises the following steps:

s1, weighing ZrFe (with 90wt.% of Zr content and the balance of Fe and unavoidable impurities) with purity of more than or equal to 99.90wt.%, moFe (with the balance of Fe and unavoidable impurities) and high-purity ingots of Ti (Mo: zr: fe: ti=11.38:6.20:1.80:80.52) according to mass percent, and putting the ingots into an electroslag furnace for smelting, cooling and forging to obtain bars with diameter of 50mm, length of 700mm and front end of 90 DEG cone angle;

s2, carrying out vacuum gas atomization on the bar obtained in the S1 by using electrode induction melting under the protection of crucible-free high-purity argon (99.999 vol.%) to prepare powder, setting the feeding amount to be 200mm/min, carrying out rotating speed to be 20r/min, selecting high-pressure (supersonic) high-purity argon (99.999 vol.%) as powder blowing gas, and carrying out atomization powder blowing under the pressure of 1.0MPa to obtain Ti-Mo-Zr-Fe alloy powder;

s3, putting the spherical Ti-Mo-Zr-Fe alloy powder with D50=45 mu m, the particle size distribution of which is 15-53 mu m and spherical pure copper powder with the particle size of 500nm, the purity of which is more than or equal to 99.90 wt%, into a planetary ball mill according to the proportion, ball milling and mixing powder, wherein the ball milling tank is filled with 1/2 of absolute ethyl alcohol (the purity of which is 99%) serving as a liquid medium, 1/2 of the residual tank volume is filled with high-purity argon (99.999 vol%) for 1 hour, the mixing time is 1.5 hours, the rotating speed is 200r/min, the mass ratio of the spherical materials is 3:1, vacuum drying is carried out, the vacuum pressure is = -0.1bar, the heat preservation temperature is = 100 ℃, the heating rate is 80 ℃/min, the heat preservation time is 2 hours, then the temperature is reduced to 25 ℃, and the Ti-Mo-Zr-Fe-xCu powder is obtained, and the high-strength antibacterial titanium alloy material for manufacturing is put into a vacuum bag for vacuum pumping and preservation.

Example 2

s3, putting the spherical Ti-Mo-Zr-Fe alloy powder with D50=45 mu m, the particle size distribution of which is 15-53 mu m and the spherical pure copper powder with the particle size of 500nm, the purity of which is more than or equal to 99.90 wt%, into a planetary ball mill according to the proportion, ball milling and mixing the powder, wherein the ball milling tank is filled with 1/2 of absolute ethyl alcohol (the purity of which is 99%) serving as a liquid medium, 1/2 of the residual tank volume is filled with high-purity argon (99.999 vol%) for 1 hour, the mixing time is 1.5 hours, the rotating speed is 200r/min, the mass ratio of the spherical material is 3:1, vacuum drying is carried out, the vacuum pressure is = -0.1bar, the heat preservation temperature is = 100 ℃, the heating rate is = 80 ℃/min, the heat preservation time is 2 hours, then the temperature is reduced to 25 ℃, and the Ti-Mo-Zr-Fe-xCu powder is obtained, and the high-strength antibacterial titanium alloy material for manufacturing is put into a vacuum bag for vacuum pumping preservation.

Example 3

Comparative example 1

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: in comparison with example 1, this comparative example lacks copper element.

Comparative example 2

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: the copper element content of this comparative example was 1wt.% compared to example 1.

Comparative example 3

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: the copper element content of this comparative example was 7wt.% compared to example 1.

Comparative example 4

s1, weighing Zr, fe, mo, ti and Cu high-purity ingots with the purity of more than or equal to 99.90wt.% according to mass percentage, putting the ingots into an electroslag furnace for smelting, cooling and forging to obtain bars with the diameter of 50mm, the length of 700mm and the front end of 90-degree cone angle;

s2, carrying out vacuum gas atomization on the bar obtained in the step S1 by using electrode induction melting under the protection of crucible-free high-purity argon (99.999 vol.%) to prepare powder, setting the feeding amount to be 200mm/min, carrying out rotating speed to be 20r/min, selecting high-pressure (supersonic) high-purity argon (99.999 vol.%) as powder blowing gas, and carrying out atomization powder blowing under the pressure of 1.0MPa to obtain Ti-Mo-Zr-Fe-xCu alloy powder.

Comparative example 5

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: in comparison with example 1, the atomizing blowing pressure of this comparative example S2 was 0.2MPa.

Comparative example 6

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: in comparison with example 1, the atomizing blowing pressure of this comparative example S2 was 1.3MPa.

Comparative example 7

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 1, except that: compared with example 1, the spherical pure copper powder of this comparative example S3 had a particle diameter of 11 to 73. Mu.m.

Comparative example 8

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 2, except that: compared with example 2, the spherical pure copper powder of this comparative example S3 had a particle diameter of 11 to 73. Mu.m.

Comparative example 9

A method for preparing a high-strength antibacterial titanium alloy material for additive manufacturing, the procedure not specifically described is the same as that of example 3, except that: compared with example 3, the spherical pure copper powder of this comparative example S3 had a particle diameter of 11 to 73. Mu.m.

Specific element contents and parameters of examples 1 to 3 and comparative examples 1 to 9 are shown in Table 1.

TABLE 1 element content and parameter settings for examples 1 to 3 and comparative examples 1 to 9

Using Solidworks three-dimensional modeling software to build a 3D model of an alloy material, then introducing the model into Magics software to place parts and set a laser scanning sequence, pouring the Ti-Mo-Zr-Fe-xCu powders obtained in examples 1-3 and comparative examples 1-9 into a powder storage bin of a laser selective melting additive manufacturing system, manufacturing and forming by using an EOS M290 system manufactured by EOS GmbH company of Germany through an SLM (Selective Laser Melting, laser selective melting) technology, wherein a laser spot=100 μm, a laser power=100W, a layer thickness=30 μm, a scanning interval=90 μm, a scanning speed=550 mm/s, and a zigzag scanning mode to obtain a test sample.

Wherein, since the powder stability of comparative example 4 is extremely poor, the irregular powder blown out in comparative example 5 is more, the powder satellite blown out in comparative example 6 is extremely numerous and extremely irregular, and is not suitable for laser 3D printing, and the test sample cannot be obtained and tested in powder form.

The performance test is carried out on the samples, and the specific test process is as follows:

(1) Microstructure testing

FIG. 1 is a microstructure morphology of Ti-Mo-Zr-Fe-xCu after the powder obtained in example 1 is shaped by SLM, the grain structure is fine, cu particles are not enriched or segregated, and the SLM melting channel is fine, so that the solidification process is not affected by the addition of Cu particles.

Characterization test results for the remaining examples are substantially identical to those of example 1.

The comparative example 4 is directly prepared by using Zr, fe, mo, ti and high-purity ingots of Cu elements, the melting point of Mo is higher (about 2623 ℃), but the boiling point of Fe is about 2750 ℃, the boiling point of Cu is about 2567 ℃, the melting temperature is required to be accurately maintained to ensure that the elements Fe and Cu cannot be evaporated, partial segregation phenomenon caused by partial Mo in the prepared bar is not melted, the density of Cu is much higher than that of Ti, the density of Cu is close to 2 times that of Ti, obvious segregation occurs in the components of the bar when the bar is sampled at different positions, and the average components of Mo at the positions of a material head, a material middle and a material tail are respectively about: 7.85wt.%, 9.12wt.%, and 11.23wt.%, the average composition of Cu also had large deviations, and the stability and consistency of the powder produced were extremely poor and laser 3D printing could not be performed.

In comparative example 5, the blowing pressure in step S2 was set to 0.2MPa, and the remaining parameters were unchanged, and since the blowing pressure was low, the amount of irregular powder blown out was large, and as shown in fig. 2, the powder yield suitable for 3D printing in the 15-75 μm particle size interval was low.

In comparative example 6, the blowing pressure in step S2 was set to 1.3MPa, and the remaining parameters were unchanged, and since the blowing pressure was too high, the blown powder satellites were extremely large and irregular, as shown in fig. 3, and were not suitable for laser 3D printing.

The Cu particles in the step S4 of the comparative examples 7-9 are 10-73 mu m, the rest parameters are unchanged, and although sphericity after powder mixing is not affected, the particle sizes of the Cu particles and the Cu particles are not greatly different, and a large number of holes are formed in a microstructure after 3D printing and forming, so as to obviously observe unmelted Cu particles in the microstructure after 3D printing of the Ti-Mo-Zr-Fe-xCu powder prepared in the comparative example 6, which leads to rapid reduction of mechanical properties after printing and is not suitable for medical appliances at large bearing parts as shown in fig. 4.

(2) Mechanical property test

The samples prepared in examples 1 to 3 and comparative examples 1 and comparative examples 7 to 9 were subjected to stress-strain performance test at room temperature (25 ℃) stretching, and the test method was: tensile testing was performed at a displacement rate of 1mm/min at room temperature according to ASTM E8M standard. Mechanical properties including tensile strength (UTS), yield Strength (YS) and strain at break were read directly from the INSTRON tensile tester and strain failure was evaluated by a 10mm range strain gauge and electronic extensometer mounted on the gauge portion of the test specimen. The modulus of elasticity was calculated from the stress-strain curve. For each experimental group, three samples were tested and the average was calculated.

The samples prepared in examples 1 to 3 and comparative examples 1 and comparative examples 7 to 9 were subjected to an average microhardness test by: the vickers microhardness of the test specimens was measured using a microhardness tester (model Leitz Wetzlar, germany) with a load of 200g and a loading time of 25s. Polishing the surface roughness of the test surface of the SLM sample to below 0.15 mu m, measuring microhardness values of different positions of the surface of the SLM sample, measuring for 10 times, and taking an average value. The test results are shown in Table 2.

Table 2 mechanical properties of examples 1 to 3 and comparative example 1, comparative examples 6 to 8

As can be seen from Table 2, the high-strength antibacterial titanium alloy materials for additive manufacturing in examples 1-3 of the present invention have excellent hardness and lower elastic modulus, and although the mechanical properties are somewhat reduced with the increase of the copper element content, the comprehensive mechanical properties are excellent, and the high-strength antibacterial titanium alloy material is suitable for biomedical high-end instruments and other aspects; in contrast, comparative example 1, in which no copper element was added, had an elastic modulus of 88.7GPa, and the pure copper powders used in comparative examples 6 to 8 had excessively large particle diameters, and produced a large amount of hard particles such as Ti-Cu, which caused a sharp decrease in elongation after breaking, and the prepared samples had an elastic modulus of 70GPa or more, which was not suitable for medical materials.

(3) Biological Performance test

The samples prepared in examples 1-3 and comparative examples 1-3 were subjected to in vitro cytotoxicity, proliferation and differentiation effect tests.

The MC3T3-E1 osteoblast precursor cells are adopted for analysis, and the international standard ISO 10993-5 is met. Before use in cytotoxicity assays, liquid extracts of samples (37 ℃ C., 10% FBS (v/v) in. Alpha. -MEM, 3 cm) were prepared ² /mL) and filter sterilized, which was evaluated for cytotoxicity using a cell counting kit-8 (CCK-8). BMSCs at 1X 10 per well ⁴ Density of individual cells was seeded on 96-well plates (Nest, USA) for one day and then medium was replaced with medical grade polyethylene (negative control, no cytotoxicity), alpha-MEM (positive control with 10% FBS (v/v) and 10% dimethyl sulfoxide (DMSO), liquid extract providing reproducible cytotoxicity reaction and liquid extract from each group (100. Mu.L/well) of SLM Ti-Mo-Zr-Fe-xCu samples for 1, 3, 5 daysAnd 7 days. Subsequently, 10. Mu.L of CCK-8 solution was added to each well of the plate, and the plate was incubated under light for two hours. The absorbance at 450nm was measured. The values for the negative control wells were averaged and taken as 100% cell viability. All other values were then averaged over their groups and compared to the negative control group.

The test method for staphylococcus aureus resistance is as follows:

LB liquid culture medium-measuring 100mL distilled water with a measuring cylinder, pouring into a 250mL reagent bottle, weighing 2.5g LB broth culture medium respectively by an analysis electronic day, adding and mixing uniformly, sterilizing in a high-temperature high-pressure steam sterilizing pot at 121 ℃ for 15min for later use.

LB solid culture medium-100 mL distilled water is measured by a measuring cylinder and poured into a 250mL reagent bottle, 2.5g LB broth culture medium and 1.5g agar powder are respectively weighed by an analysis electronic day, the weighed reagents are added and uniformly mixed, and then the mixture is sterilized in a high-temperature high-pressure steam sterilizing pot at 121 ℃ for 15 min. After the medium is cooled to about 40-50 ℃,15 mL of the medium is sucked by an electric pipette and poured into a disposable sterile plate.

2 bacterial culture tubes (12 mL) were taken, 3mL of LB liquid medium was added to each tube, and a single colony was picked from a solid medium of Staphylococcus aureus and added to the liquid medium, and the other was used as a blank control. Shaking culture was carried out overnight (15 h) with a constant temperature shaker (37 ℃ C., 200 rpm).

Wiping the surface of the sample with 75% alcohol cotton, drying, and placing into disposable petri dishes with corresponding numbers, and sterilizing both sides with ultraviolet irradiation for 30 min.

The staphylococcus aureus bacterial liquid is diluted to 106CFU/mL by LB liquid culture medium. 50 mu L of diluted bacterial liquid is dripped on the surface of the sample, and no sample is added in a control group. Covered with a cover film and pressed gently. Placing in a constant temperature incubator at 37 ℃ for static culture for 18h.

After the completion of the incubation, 2mL of sterile PBS was used for rinsing, and 10-fold serial dilutions were made with PBS solution, and 100. Mu.L of the dilutions were spread evenly on LB solid medium. Culturing in a constant temperature incubator at 37 ℃ for 18 hours, taking out, photographing and recording the colony number. Colony counts were then performed and the antimicrobial rates calculated according to GB 4789.2-2016.

The specific test results of each example and comparative example are shown in table 3.

TABLE 3 biological Properties of examples 1-3 and comparative examples 1-3

As can be judged from table 3, the high-strength antibacterial titanium alloy material for additive manufacturing of examples 1 to 3 of the present invention has no cytotoxicity, and shows excellent antibacterial property and bone-promoting effect, not only has a remarkable improvement of the sterilization effect with the continuous increase of Cu element, but also has a gain effect on the differentiation and proliferation of MC3T3-E1 osteoblasts; the comparative example 1, which is free of copper element and has no antibacterial property, the comparative example 2 has a copper element content of 1.0wt.%, has low antibacterial rate and no obvious effect on promoting the growth of MC3T3 cells, the comparative example 3 has a copper element content of 7.0wt.%, and has an antibacterial rate of 99.5%, but the survival rate of MC3T3 cells is greatly reduced by 25.2%, which indicates that the increase of Cu element has a great inhibitory effect on the growth of cell membranes, resulting in poor biocompatibility.

FIG. 5 shows that the Ti-Mo-Zr-Fe-xCu porous structure material developed by the patent is not abnormal after being implanted in a rat body for 3 months, and the Ti-Mo-Zr-Fe-xCu porous structure is found to have a phenomenon of obvious new bone ingrowth (shown by a dark color part) after being implanted in the rat body for 12 weeks and taken out for CT test, so that excellent osseointegration is shown, and the personalized SLM Ti-Mo-Zr-Fe-xCu alloy which is developed in a proper Cu content range and has excellent comprehensive mechanical property and biological activity has excellent potential and good application prospect of developing products.

In conclusion, the high-strength antibacterial titanium alloy material for additive manufacturing effectively reduces the elastic modulus of the titanium alloy material, has high hardness, few impurities, high alloy purity, controllable oxygen content below 1000ppm, good weldability and formability, excellent biocompatibility, and capabilities of enhancing the antibacterial infection resistance of the material and promoting the bioactivity, enables the traditional titanium alloy to be converted into a bioactive material from a bio-inert material, is suitable for various additive manufacturing technologies such as laser selective melting, selective laser sintering and the like as a medical material, and expands the application scope of materials in the field of additive manufacturing.

Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. The high-strength antibacterial titanium alloy material for additive manufacturing is characterized by comprising the following element components in percentage by mass:

2. A method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 1, which comprises the following steps:

3. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: the purity of the high-purity ingots of ZrFe, moFe and Ti described in S1 is more than or equal to 99.90 wt%.

4. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: s3, the purity of the pure copper powder is more than or equal to 99.90 wt%.

5. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: s2, vacuum gas atomization is carried out under the protection of argon, and the temperature is 1800-2000 ℃.

6. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: the grain diameter of the Ti-Mo-Zr-Fe alloy powder in S3 is 35-65 mu m, and the grain diameter of the pure copper powder is 200 nm-10 mu m.

7. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: and S3, carrying out ball milling powder mixing under the protection of argon for 1-2 hours, wherein the rotating speed is 150-250 r/min, and the mass ratio of the ball materials is (3-5): 1.

8. The method for preparing the high-strength antibacterial titanium alloy material for additive manufacturing according to claim 2, wherein the method comprises the following steps of: s3, the vacuum drying temperature is 80-150 ℃ and the pressure is-0.8-0.1 bar.

9. A high-strength antimicrobial titanium alloy material for additive manufacturing according to any one of the preceding claims for laser 3D printing.