Modified titanium-tantalum alloy material, surface modification method and application thereof

Abstract

The present application relates to a modified titanium-tantalum alloy material and a surface modification method and application. The modified titanium-tantalum alloy material comprises a titanium-tantalum alloy substrate, and a titanium dioxide film is attached to the surface of the titanium-tantalum alloy substrate. The present application also provides a surface modification method of the modified titanium-tantalum alloy material, comprising the following steps: placing a titanium-tantalum alloy substrate in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropyl alcohol and water, and performing a hydrothermal reaction; placing the titanium-tantalum alloy substrate after the hydrothermal reaction in an alkaline solution for soaking, so as to perform fluorine ion replacement, and cleaning to obtain an intermediate product; and performing low-temperature plasma treatment on the intermediate product in a mixed atmosphere of argon and oxygen, to obtain a titanium-tantalum alloy with a biologically active titanium dioxide film attached to the surface. The present application provides the application of the modified titanium-tantalum alloy material as a biomedical material. The present application solves the problem that the existing titanium-tantalum alloy material has low biological activity as a biomedical material.

Description

Technical Field

[0001] This invention relates to the field of biomedical nanomaterials technology, specifically to a modified titanium-tantalum alloy material, its surface modification method, and its applications. Background Technology

[0002] According to incomplete statistics, more than one million patients undergo joint replacement surgery in my country each year, creating a significant demand for bone tissue repair materials. Biomedical metallic materials possess high mechanical strength, hardness, and good toughness, impact resistance, and fatigue resistance, making them widely used as materials for repairing and replacing human hard tissues. Among numerous biomedical metallic materials, titanium (Ti) and its alloys have become the preferred choice for replacing and repairing human hard tissues due to their superior comprehensive mechanical properties, strong corrosion resistance, good biocompatibility, ease of processing, and low cost. Compared to Ti, tantalum (Ta) exhibits better corrosion resistance, superior biocompatibility, and an elastic modulus more compatible with bone tissue, thus becoming a new material for bone repair that has received considerable attention in recent years. However, the scarcity of tantalum resources leads to its high price, and its high melting point and processing difficulties greatly limit its widespread application in the biomedical field. Constructing titanium-tantalum alloy implant materials with titanium as the main component can effectively reduce the elastic modulus of pure titanium, fully utilize the advantages of tantalum's high corrosion resistance and good biocompatibility, and overcome the limitation of high price of pure tantalum. It is one of the key research and development directions in the field of biomedical materials in the future.

[0003] However, like other titanium alloys, titanium-tantalum alloys have limited osteogenic bioactivity on their surface, and it typically takes a long time for them to establish a stable chemical bond with the surrounding bone tissue after implantation. Therefore, to reduce the risk of implantation failure due to displacement and loosening in the early stages of implantation, it is essential to modify them to improve their bioactivity and thus accelerate the formation of a strong biochemical bond with bone tissue. Summary of the Invention

[0004] The purpose of this invention is to provide a modified titanium-tantalum alloy material, a surface modification method, and its application, in order to solve the problem of low bioactivity of existing titanium-tantalum alloy materials as biomedical materials.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A modified titanium-tantalum alloy material includes a titanium-tantalum alloy matrix, wherein a titanium dioxide (TiO2) film is attached to the surface of the titanium-tantalum alloy matrix.

[0007] Preferably, a modified titanium-tantalum alloy material is composed of a titanium-tantalum alloy substrate and a titanium dioxide (TiO2) film attached to the surface of the titanium-tantalum alloy substrate.

[0008] Based on the above-mentioned technical means, by attaching a titanium dioxide (TiO2) film to a titanium-tantalum alloy substrate and then using it as a biomedical material, the titanium dioxide (TiO2) film can induce calcium and phosphorus ions to rapidly deposit on the surface of the titanium-tantalum alloy substrate in the form of hydroxyapatite under physiological conditions, forming a gradient interface structure of titanium-tantalum alloy-titanium dioxide-hydroxyapatite. This can effectively improve the bonding effect between the implant material and human bone tissue, thereby accelerating the healing process between the implant and the hard tissue. This effectively solves the problem of low bioactivity of existing titanium-tantalum alloy materials as biomedical materials. At the same time, the titanium-tantalum alloy substrate can not only effectively reduce the elastic modulus of pure titanium, but also effectively overcome the problem of high price of pure tantalum, and has the advantages of strong corrosion resistance and good biocompatibility.

[0009] Preferably, the titanium dioxide (TiO2) film is bioactive, the thickness of the titanium dioxide (TiO2) film is between 2 μm and 4 μm, and the titanium dioxide (TiO2) film is composed of particles with a particle size between 2 μm and 4 μm.

[0010] Preferably, the titanium dioxide (TiO2) film is a micron-sized aggregate formed by the self-assembly of truncated single crystals with exposed {001} crystal planes, and is grown in situ on the surface of a titanium-tantalum alloy substrate.

[0011] Preferably, the titanium dioxide (TiO2) film on the surface of the titanium-tantalum alloy substrate has anatase TiO2 crystal phase composition, and the tantalum oxide exists in an amorphous form.

[0012] Preferably, each of the particles is composed of multiple titanium dioxide (TiO2) single crystals self-assembled from exposed (001) crystal faces;

[0013] The titanium dioxide (TiO2) single crystal has a truncated octahedral configuration. The titanium dioxide (TiO2) single crystal is composed of eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal planes is 100nm~400nm.

[0014] Measurements showed that the titanium dioxide (TiO2) film on the surface of the titanium-tantalum alloy substrate consisted of particles with a diameter between 2 μm and 4 μm, and each particle was formed by the self-assembly of multiple exposed (001) crystal plane titanium dioxide (TiO2) single crystals. This larger-scale micron-sized aggregate, formed by the self-assembly of multiple titanium dioxide (TiO2) single crystals, exhibits high roughness, high surface energy, and strong hydrophilicity, thus facilitating the wetting, spreading, and interaction of active ions in body fluids on its surface.

[0015] Preferably, the composition of the titanium-tantalum alloy matrix includes 10% to 30% tantalum (Ta) by mass percentage, with the balance being titanium and unavoidable impurities.

[0016] Experimental studies have shown that excessive tantalum (Ta) content leads to difficulties in processing and high costs in the alloy. Furthermore, excessive tantalum (Ta) content can hinder the formation of exposed (001) high-energy TiO2 thin films due to tantalum's high inertness. Therefore, the mass percentage of tantalum (Ta) in the titanium-tantalum alloy matrix should be controlled between 10% and 30%.

[0017] The present invention also provides a surface modification method for modified titanium-tantalum alloy materials as described herein, comprising the following steps:

[0018] S1. The titanium-tantalum alloy matrix is ​​placed in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol and water to carry out a hydrothermal reaction.

[0019] S2. The titanium-tantalum alloy matrix after hydrothermal reaction is immersed in an alkaline solution to perform fluoride ion replacement and cleaning to obtain an intermediate product.

[0020] S3. The intermediate product is subjected to low-temperature plasma treatment in a mixed atmosphere of argon (Ar) and oxygen (O2) to obtain a titanium-tantalum alloy with a bioactive titanium dioxide (TiO2) film attached to its surface.

[0021] According to the above-mentioned technical means, a titanium-tantalum alloy substrate is placed in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol, and water for hydrothermal reaction. In this process, the titanium-tantalum alloy substrate serves both as a carrier for the surface oxide film and as a source of material for its growth. Specifically, the surface layer of the titanium-tantalum alloy substrate first reacts with the solvent to generate water-soluble complex ions. These complex ions then undergo complex hydrolysis, dehydration, nucleation, and growth to obtain a crystallized titanium dioxide (TiO2) film with a specific morphology, high roughness, high surface energy, and strong hydrophilicity. This film is then placed in an alkaline solution for fluoride ion replacement, followed by low-temperature plasma treatment in a mixed atmosphere of argon and oxygen to further increase the hydroxyl content on the surface of the titanium dioxide (TiO2) film. This effectively enhances the inductive ability of the modified titanium-tantalum alloy material and lowers the energy barrier required to overcome for the formation of apatite crystal nuclei by calcium and phosphorus ions in the body fluid. This technical means also has the advantages of simple surface modification processes, ease of industrial scale-up, and the use of environmentally friendly and non-corrosive raw materials.

[0022] Destroying the spontaneously generated, non-uniform, thin-film passivation layer on the surface of a titanium-tantalum alloy substrate and reconstructing an active TiO2 film as a transition layer is an effective method to improve its surface bioactivity. The principle is that, under physiological conditions, the active TiO2 film can induce the rapid deposition of calcium and phosphorus ions in the form of hydroxyapatite on the surface of the titanium-tantalum alloy substrate, forming a gradient interface structure of titanium-tantalum alloy-titanium dioxide-hydroxyapatite. This effectively improves the bonding effect between the implant material and human bone tissue, thereby accelerating the healing process between the implant and the hard tissue. Furthermore, studies have confirmed that the ability of the TiO2 film to induce hydroxyapatite formation is closely related to its surface morphology, roughness, degree of crystallization, surface hydroxyl content, surface charge, and chemical composition. TiO2 films with high roughness, high surface energy, abundant hydroxyl content, and high degree of crystallization exhibit better surface bioactivity.

[0023] Preferably, step S1 specifically includes: polishing the titanium-tantalum alloy substrate with sandpaper, ultrasonically degreasing it in anhydrous ethanol, cleaning it with deionized water, and air-drying it naturally; then placing the titanium-tantalum alloy substrate in a hydrothermal reactor with a polytetrafluoroethylene liner, the hydrothermal reactor containing a mixed solution of hydrogen peroxide-isopropanol-H2O containing dissolved ammonium fluoride, sealing the hydrothermal reactor and placing it in an oven to carry out the hydrothermal reaction.

[0024] Preferably, in step S1, polishing the titanium-tantalum alloy substrate with sandpaper includes polishing it to a bright finish with 150#, 600# and 1000# sandpaper in sequence.

[0025] Preferably, in step S1, the volumetric filling degree of the hydrothermal reactor is 40% to 60%.

[0026] Preferably, step S2 specifically includes: after the hydrothermal reaction is completed, the hydrothermal reactor is removed from the oven and allowed to cool naturally. The titanium-tantalum alloy substrate after the hydrothermal reaction is then removed and immersed in an alkaline solution to replace fluoride ions. Subsequently, it is removed and rinsed with deionized water until the pH value of the washing solution is close to neutral. It is then air-dried naturally to obtain a titanium-tantalum alloy substrate / TiO2 film with no fluoride ion residue on the surface.

[0027] In alkaline solution, fluoride ions adsorbed on the surface of the thin film obtained by hydrothermal reaction can react with OH-. - Ions undergo a substitution reaction to form Ti-OH. It is generally believed that the induction of hydroxyapatite by crystalline TiO2 is attributed to the effect of surface hydroxyl groups. That is, under physiological conditions, hydroxyl groups deprotonate to form Ti-O. - To maintain surface neutrality, Ti-O - It will attract Ca from body fluids through electrostatic attraction. 2+ This leads to the adsorption of OH groups in body fluids. - and PO4 3- This makes [Ca] near the surface of the thin film...2+ ]、[PO4 3- ]、[OH - When the plasma concentration increases to a supersaturated state, the initial nuclei of hydroxyapatite are formed, which in turn induces ions in the body fluid to rapidly precipitate on the film surface in the form of apatite.

[0028] Preferably, step S3 specifically includes: placing a titanium-tantalum alloy substrate / TiO2 film with no residual fluorine ions on its surface into a low-temperature plasma treatment instrument for treatment in an Ar / O2 mixed atmosphere to obtain a titanium-tantalum alloy sheet with a bioactive TiO2 film on its surface, i.e., a modified titanium-tantalum alloy material.

[0029] Preferably, in step S1, before the titanium-tantalum alloy substrate is placed in the mixed solution, a thin passivation film on the surface of the titanium-tantalum alloy substrate is removed.

[0030] Preferably, in step S1, the concentration of ammonium fluoride in the mixed solution is 60 mmol / L to 100 mmol / L.

[0031] Preferably, in step S1, the volume percentage of hydrogen peroxide in the mixed solution is 30% to 50%.

[0032] Preferably, in S1, the volume percentage of isopropanol in the mixed solution is 20% to 40%.

[0033] Preferably, in step S1, the temperature of the hydrothermal reaction is 180℃~200℃.

[0034] Preferably, in step S1, the hydrothermal reaction time is 30h to 72h.

[0035] Preferably, in S2, the alkaline solution is selected from sodium hydroxide (NaOH) solution and / or potassium hydroxide (KOH) solution.

[0036] Preferably, in step S2, the concentration of alkali in the alkaline solution is 1 mol / L to 2 mol / L.

[0037] Preferably, in step S2, the soaking time is 24h to 48h.

[0038] Preferably, in step S2, the cleaning process involves rinsing with deionized water until the pH of the washing solution is near neutral. The near-neutral pH range is 6.5 to 7.5.

[0039] Preferably, in step S3, the volume percentage of oxygen in the mixed atmosphere is 8% to 12%.

[0040] Pure oxygen can also be used instead of mixed atmosphere.

[0041] Preferably, in step S3, the gas flow rate of the mixed atmosphere is 3L / min to 6L / min.

[0042] Preferably, in step S3, the power of the low-temperature plasma treatment is 100~300W.

[0043] Preferably, in step S3, the low-temperature plasma treatment time is 10~30 min.

[0044] Preferably, the volume percentage of oxygen in the mixed atmosphere is 10%.

[0045] The present invention also provides an application of the modified titanium-tantalum alloy material as described herein, wherein the modified titanium-tantalum alloy material is used as a biomedical material.

[0046] Studies have shown that modified titanium-tantalum alloy materials have strong bioactivity and the ability to rapidly induce the precipitation of calcium and phosphorus ions in body fluids as hydroxyapatite. Therefore, using the modified titanium-tantalum alloy material of this invention as a biomedical material can help form a strong chemical bond between the modified titanium-tantalum alloy material as an implant material and human bone tissue, thereby effectively shortening the patient's recovery time.

[0047] Preferably, the modified titanium-tantalum alloy material is used as a bone tissue repair material in biomedical materials.

[0048] The beneficial effects of this invention are:

[0049] 1) The modified titanium-tantalum alloy material of the present invention is used as a biomedical material by attaching a titanium dioxide (TiO2) film to a titanium-tantalum alloy substrate. This titanium dioxide (TiO2) film has the ability to rapidly induce the precipitation of calcium and phosphorus ions in body fluids as calcium hydroxyphosphate salts under physiological conditions. By rapidly depositing hydroxyapatite on the surface of the titanium-tantalum alloy substrate to form a gradient interface structure of titanium-tantalum alloy-titanium dioxide-hydroxyapatite, it is beneficial to promote the formation of a strong chemical bond between the implant material and human bone tissue, thereby ensuring the bonding effect and accelerating the healing process between the implant and the hard tissue, effectively shortening the patient's recovery time. At the same time, the titanium-tantalum alloy substrate not only effectively reduces the elastic modulus of pure titanium but also effectively overcomes the problem of high price of pure tantalum, and has the advantages of strong corrosion resistance and good biocompatibility.

[0050] 2) The surface modification method of the modified titanium-tantalum alloy material of the present invention involves placing the titanium-tantalum alloy substrate in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol and water for hydrothermal reaction. The titanium-tantalum alloy substrate serves as both a carrier for the surface oxide film and a source of material for oxide film growth. The process involves reacting the titanium-tantalum alloy substrate with a solvent to generate water-soluble complex ions. These complex ions then undergo complex hydrolysis, dehydration, nucleation, and growth to obtain a crystallized titanium dioxide (TiO2) film with a specific morphology. The film is then placed in an alkaline solution for fluoride ion replacement to grow the TiO2 film in situ on the surface of the titanium-tantalum alloy substrate. This effectively ensures the bonding ability between the TiO2 film and the titanium-tantalum alloy substrate and the structural stability of the transition layer. Finally, the film undergoes low-temperature plasma treatment in a mixed atmosphere of argon and oxygen to further increase the hydroxyl content on the surface of the TiO2 film. This effectively enhances the induction ability of the modified titanium-tantalum alloy material, reduces the energy barrier required for apatite nucleation, and offers advantages such as simple surface modification process, ease of industrial scale-up, and environmentally friendly and non-corrosive raw materials.

[0051] 3) Because the modified titanium-tantalum alloy material has strong bioactivity and the ability to rapidly induce the precipitation of calcium and phosphorus ions in body fluids as hydroxyapatite, using the modified titanium-tantalum alloy material of this invention as a biomedical material can help the modified titanium-tantalum alloy material form a strong chemical bond with human bone tissue as an implant material, thereby effectively shortening the recovery time of patients. It has promotion and application value in the field of biomedical nanomaterials technology. Detailed Implementation

[0052] The following description, with reference to preferred embodiments, illustrates the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be understood that the preferred embodiments are merely illustrative of the present invention and not intended to limit the scope of protection of the present invention.

[0053] This application aims to disclose a modified titanium-tantalum alloy material, its surface modification method, and its application.

[0054] Among them, the modified titanium-tantalum alloy material includes a titanium-tantalum alloy matrix, on the surface of which a titanium dioxide (TiO2) film is attached.

[0055] In some embodiments, the modified titanium-tantalum alloy material consists of a titanium-tantalum alloy substrate and a titanium dioxide (TiO2) film attached to the surface of the titanium-tantalum alloy substrate.

[0056] In some embodiments, the titanium dioxide (TiO2) film is bioactive and is attached to the surface of a titanium-tantalum alloy substrate, serving as a biomedical material. Under physiological conditions, the titanium dioxide (TiO2) film can induce the rapid deposition of calcium and phosphorus ions in the form of hydroxyapatite on the surface of the titanium-tantalum alloy substrate, forming a gradient interface structure of titanium-tantalum alloy-titanium dioxide-hydroxyapatite. This effectively improves the bonding effect between the implant material and human bone tissue, thereby accelerating the healing process between the implant and the hard tissue. The thickness of the titanium dioxide (TiO2) film is between 2 μm and 4 μm. The titanium dioxide (TiO2) film is composed of particles with a particle size between 2 μm and 4 μm.

[0057] For example, the titanium dioxide (TiO2) film is a micron-sized aggregate formed by the self-assembly of truncated single crystals with exposed {001} crystal planes, and is grown in situ on the surface of a titanium-tantalum alloy substrate. The larger-scale micron-sized aggregates formed by the self-assembly of multiple titanium dioxide (TiO2) single crystals have the characteristics of large roughness, high surface area and strong hydrophilicity, which is conducive to the wetting, spreading and action of active ions in body fluids on their surface.

[0058] In some embodiments, the titanium dioxide (TiO2) film on the surface of the titanium-tantalum alloy substrate has anatase TiO2 crystal phase composition, and the tantalum oxide exists in an amorphous form.

[0059] In some embodiments, a single particle is composed of a plurality of titanium dioxide (TiO2) single crystals self-assembled from exposed (001) crystal faces;

[0060] Titanium dioxide (TiO2) single crystal has a truncated octahedral configuration. The titanium dioxide (TiO2) single crystal is composed of eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 100nm~400nm.

[0061] For example, the composition of the titanium-tantalum alloy matrix includes 10% to 30% tantalum (Ta) by mass percentage, with the balance being titanium and unavoidable impurities. The mass percentage of tantalum in the titanium-tantalum alloy matrix can be any possible value of 10%, 15%, 20%, 25%, 30%, or 10% to 30%.

[0062] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0063] S1. The titanium-tantalum alloy matrix is ​​placed in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol and water to carry out a hydrothermal reaction.

[0064] S2. The titanium-tantalum alloy matrix after hydrothermal reaction is immersed in an alkaline solution to perform fluoride ion replacement and cleaning to obtain an intermediate product.

[0065] S3. In order to increase the hydroxyl content on the surface of the titanium dioxide (TiO2) film to improve the induction ability of the modified titanium-tantalum alloy material and reduce the energy barrier required to overcome the nucleation of apatite, the intermediate product was subjected to low-temperature plasma treatment in a mixed atmosphere of argon and oxygen to obtain a titanium-tantalum alloy with a bioactive titanium dioxide (TiO2) film attached to the surface.

[0066] In some embodiments, S1 specifically includes: polishing the titanium-tantalum alloy sheet substrate with sandpaper, ultrasonically degreasing it in anhydrous ethanol, cleaning it with deionized water, and air-drying it to effectively remove the thin passivation film on the surface of the titanium-tantalum alloy sheet, thereby improving the bonding strength between the titanium-tantalum alloy sheet substrate and the titanium dioxide (TiO2) film obtained by the subsequent hydrothermal reaction; then placing the titanium-tantalum alloy sheet substrate in a hydrothermal reactor with a polytetrafluoroethylene liner, the hydrothermal reactor containing a mixed solution of hydrogen peroxide-isopropanol-H2O containing dissolved ammonium fluoride, sealing the hydrothermal reactor and placing it in an oven to carry out the hydrothermal reaction.

[0067] For example, in S1, polishing the titanium-tantalum alloy sheet substrate with sandpaper includes polishing it to a bright finish with 150#, 600# and 1000# sandpaper in sequence.

[0068] For example, in S1, the volumetric filling degree of the hydrothermal reactor is 40% to 60%. The volumetric filling degree of the hydrothermal reactor can be any value between 40%, 45%, 50%, 55%, 60%, or 40% to 60%.

[0069] In some embodiments, S2 specifically includes: after the hydrothermal reaction is completed, the hydrothermal reactor is removed from the oven and allowed to cool naturally. The titanium-tantalum alloy substrate after the hydrothermal reaction is then removed and immersed in an alkaline solution to replace fluoride ions. Subsequently, it is removed and rinsed with deionized water until the pH value of the washing solution is close to neutral. It is then air-dried naturally to obtain a titanium-tantalum alloy substrate / TiO2 film with no fluoride ion residue on the surface, which is the aforementioned intermediate product.

[0070] In some embodiments, S3 specifically includes: placing a titanium-tantalum alloy substrate / TiO2 film with no residual fluorine ions on its surface into a low-temperature plasma treatment instrument for treatment in an Ar / O2 mixed atmosphere to obtain a titanium-tantalum alloy sheet with a bioactive TiO2 film on its surface, i.e., a modified titanium-tantalum alloy material.

[0071] In some embodiments, in S1, the concentration of ammonium fluoride in the mixed solution is 60 mmol / L to 100 mmol / L, and the concentration of ammonium fluoride can be selected from any possible value between 60 mmol / L, 65 mmol / L, 70 mmol / L, 75 mmol / L, 80 mmol / L, 85 mmol / L, 90 mmol / L, 95 mmol / L, 100 mmol / L or 60 mmol / L to 100 mmol / L.

[0072] For example, in S1, the volume percentage of hydrogen peroxide in the mixed solution is 30% to 50%, and the volume percentage of hydrogen peroxide can be selected from any possible value between 30%, 35%, 40%, 45%, 50%, or 30% to 50%.

[0073] For example, in S1, the volume percentage of isopropanol in the mixed solution is 20% to 40%, and the volume percentage of isopropanol can be selected from any possible value between 20%, 25%, 30%, 35%, 40%, or 20% to 40%.

[0074] For example, in S1, the temperature of the hydrothermal reaction is 180℃~200℃, and the temperature of the hydrothermal reaction can be selected from any possible value between 180℃, 185℃, 190℃, 195℃, 200℃ or 180℃~200℃.

[0075] For example, in S1, the hydrothermal reaction time is 30h to 72h, and the hydrothermal reaction time can be selected from any possible value between 30h, 36h, 42h, 48h, 54h, 60h, 66h, 72h or 30h to 72h.

[0076] In some embodiments, in S2, the alkaline solution is selected from sodium hydroxide (NaOH) solution and / or potassium hydroxide (KOH) solution.

[0077] For example, in S2, the concentration of alkali in the alkaline solution is 1 mol / L to 2 mol / L, and the concentration of alkali in the alkaline solution can be selected as any possible value between 1 mol / L, 1.5 mol / L, 2 mol / L, or 1 mol / L to 2 mol / L.

[0078] For example, in S2, the soaking time is 24h~48h, and the soaking time can be selected as any possible value between 24h, 30h, 36h, 42h, 48h or 24h~48h.

[0079] For example, in S2, the cleaning is performed by rinsing with deionized water until the pH value of the washing solution is near neutral.

[0080] In some embodiments, in S3, the volume percentage of oxygen in the mixed atmosphere is 8% to 12%, and the volume percentage of oxygen in the mixed atmosphere can be selected as any possible value between 8%, 10%, 12%, or 8% to 12%.

[0081] For example, in S3, the gas flow rate of the mixed atmosphere is 3L / min to 6L / min, and the gas flow rate of the mixed atmosphere can be selected as any possible value between 3L / min, 4L / min, 5L / min, 6L / min or 3L / min to 6L / min.

[0082] For example, in S3, the power of the low-temperature plasma treatment is 100~300W, and the power of the low-temperature plasma treatment can be selected from any possible value between 100W, 150W, 200W, 250W, 300W or 100~300W.

[0083] For example, in S3, the time for low-temperature plasma treatment is 10 to 30 minutes, and the time for low-temperature plasma treatment can be selected from any possible value between 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes or 10 to 30 minutes.

[0084] For example, the volume percentage of oxygen in the mixed atmosphere is 10%.

[0085] In some embodiments, modified titanium-tantalum alloy materials can be widely used in biomedical materials.

[0086] For example, modified titanium-tantalum alloys have high mechanical strength, hardness, and good toughness, impact resistance, and fatigue resistance, making them widely applicable as materials for the repair and replacement of human hard tissues.

[0087] Example 1

[0088] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0089] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 10%, and the balance is titanium (Ti) and other unavoidable impurities;

[0090] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 180°C for 30 hours. The mixed solution contains: ammonium fluoride at a concentration of 60 mmol / L, hydrogen peroxide at a volume percentage of 50%, isopropanol at a volume percentage of 20%, and the remainder is H2O. The reactor is 40% filled.

[0091] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and immerse it in an alkaline solution for 48 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Allow it to air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a sodium hydroxide (NaOH) solution with a sodium hydroxide (NaOH) concentration of 1 mol / L.

[0092] S4. The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on the surface obtained in S3 is placed in a low-temperature plasma treatment instrument for treatment. The treatment atmosphere is an Ar / O2 (O2 volume content is 10%) mixed gas, the flow rate of the mixed gas is 3L / min, the input power is 100W, and the treatment time is 10min. A titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on the surface is obtained, which is a modified titanium-tantalum alloy material.

[0093] According to measurements, the titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment consists of a titanium-tantalum (TiTa) alloy sheet substrate and a TiO2 film attached to the surface of the titanium-tantalum (TiTa) alloy sheet substrate. The TiO2 film consists of particles with an average particle size of 2 μm. Each particle is composed of multiple TiO2 single crystals self-assembled by exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 100 nm. The thickness of the TiO2 film is 2 μm.

[0094] The TiO2 film in this embodiment is grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0095] The titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment has anatase TiO2 crystal phase composition, and tantalum oxide exists in an amorphous form. Immersion in simulated body fluid for 7 days can induce the formation of hydroxyapatite, thus proving that the modified titanium-tantalum alloy material in this embodiment has good bioactivity.

[0096] Example 2

[0097] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0098] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 20%, and the balance is titanium (Ti) and other unavoidable impurities;

[0099] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 190°C for 60 hours. The mixed solution contains: ammonium fluoride at a concentration of 75 mmol / L, hydrogen peroxide at a volume percentage of 40%, isopropanol at a volume percentage of 30%, and the remainder is H2O. The fill factor of the hydrothermal reactor is 45%.

[0100] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and immerse it in an alkaline solution for 24 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Allow it to air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a potassium hydroxide (KOH) solution with a potassium hydroxide (KOH) concentration of 2 mol / L.

[0101] S4. The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on the surface obtained in S3 is placed in a low-temperature plasma treatment instrument for treatment. The treatment atmosphere is an Ar / O2 (O2 volume content is 10%) mixed gas, the flow rate of the mixed gas is 5L / min, the input power is 200W, and the treatment time is 20min. A titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on the surface is obtained, which is a modified titanium-tantalum alloy material.

[0102] According to measurements, the titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment consists of a titanium-tantalum (TiTa) alloy sheet substrate and a TiO2 film attached to the surface of the titanium-tantalum (TiTa) alloy sheet substrate. The TiO2 film consists of particles with an average particle size of 2.8 μm. Each particle is composed of multiple TiO2 single crystals self-assembled from exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 160 nm. The thickness of the TiO2 film is 2.8 μm.

[0103] The TiO2 film in this embodiment is grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0104] The titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment has anatase TiO2 crystal phase composition, and tantalum oxide exists in an amorphous form. Immersion in simulated body fluid for 6 days can induce the formation of hydroxyapatite, thus proving that the modified titanium-tantalum alloy material in this embodiment has good bioactivity.

[0105] Example 3

[0106] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0107] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 30%, and the balance is titanium (Ti) and other unavoidable impurities;

[0108] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 200℃ for 48 hours. The mixed solution contains: ammonium fluoride at a concentration of 75 mmol / L, hydrogen peroxide at a volume percentage of 35%, isopropanol at a volume percentage of 35%, and the remainder is H2O; the fill factor of the hydrothermal reactor is 40%.

[0109] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and immerse it in an alkaline solution for 32 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Allow it to air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a potassium hydroxide (KOH) solution with a potassium hydroxide (KOH) concentration of 2 mol / L.

[0110] S4. The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on the surface obtained in S3 is placed in a low-temperature plasma treatment instrument for treatment. The treatment atmosphere is an Ar / O2 (O2 volume content is 10%) mixed gas, the flow rate of the mixed gas is 6L / min, the input power is 300W, and the treatment time is 15min. A titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on the surface is obtained, which is a modified titanium-tantalum alloy material.

[0111] According to measurements, the titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment consists of a titanium-tantalum (TiTa) alloy sheet substrate and a TiO2 film attached to the surface of the titanium-tantalum (TiTa) alloy sheet substrate. The TiO2 film consists of particles with an average particle size of 3.2 μm. Each particle is composed of multiple TiO2 single crystals self-assembled from exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 240 nm. The thickness of the TiO2 film is 3.2 μm.

[0112] The TiO2 film in this embodiment is grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0113] The titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment has anatase TiO2 crystal phase composition, and tantalum oxide exists in an amorphous form. Immersion in simulated body fluid for 8 days can induce the formation of hydroxyapatite, thus proving that the modified titanium-tantalum alloy material in this embodiment has good bioactivity.

[0114] Example 4

[0115] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0116] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 20%, and the balance is titanium (Ti) and other unavoidable impurities;

[0117] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 180°C for 72 hours. The mixed solution contains: ammonium fluoride at a concentration of 100 mmol / L, hydrogen peroxide at a volume percentage of 40%, isopropanol at a volume percentage of 40%, and the remainder is H2O. The reactor is 60% filled.

[0118] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and soak it in an alkaline solution for 30 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Let it air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a potassium hydroxide (KOH) solution with a potassium hydroxide (KOH) concentration of 1 mol / L.

[0119] S4. The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on the surface obtained in S3 is placed in a low-temperature plasma treatment instrument for treatment. The treatment atmosphere is an Ar / O2 (O2 volume content is 10%) mixed gas, the flow rate of the mixed gas is 6L / min, the input power is 100W, and the treatment time is 30min. A titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on the surface is obtained, which is a modified titanium-tantalum alloy material.

[0120] According to measurements, the titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment consists of a titanium-tantalum (TiTa) alloy sheet substrate and a TiO2 film attached to the surface of the titanium-tantalum (TiTa) alloy sheet substrate. The TiO2 film consists of particles with an average particle size of 3.0 μm. Each particle is composed of multiple TiO2 single crystals self-assembled from exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 220 nm. The thickness of the TiO2 film is 3.0 μm.

[0121] The TiO2 film in this embodiment is grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0122] The titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment has anatase TiO2 crystal phase composition, and tantalum oxide exists in an amorphous form. Immersion in simulated body fluid for 6 days can induce the formation of hydroxyapatite, thus proving that the modified titanium-tantalum alloy material in this embodiment has good bioactivity.

[0123] Example 5

[0124] A surface modification method for modified titanium-tantalum alloy materials includes the following steps:

[0125] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 20%, and the balance is titanium (Ti) and other unavoidable impurities;

[0126] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 180°C for 72 hours. The mixed solution contains: ammonium fluoride at a concentration of 65 mmol / L, hydrogen peroxide at a volume percentage of 50%, isopropanol at a volume percentage of 20%, and the remainder is H2O. The reactor is 50% filled.

[0127] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and immerse it in an alkaline solution for 30 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Allow it to air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a sodium hydroxide (NaOH) solution with a sodium hydroxide (NaOH) concentration of 1.5 mol / L.

[0128] S4. The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on the surface obtained in S3 is placed in a low-temperature plasma treatment instrument for treatment. The treatment atmosphere is an Ar / O2 (O2 volume content is 10%) mixed gas, the flow rate of the mixed gas is 4L / min, the input power is 200W, and the treatment time is 30min. A titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on the surface is obtained, which is a modified titanium-tantalum alloy material.

[0129] According to measurements, the titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment consists of a titanium-tantalum (TiTa) alloy sheet substrate and a TiO2 film attached to the surface of the titanium-tantalum (TiTa) alloy sheet substrate. The TiO2 film consists of particles with an average particle size of 4.0 μm. Each particle is composed of multiple TiO2 single crystals self-assembled from exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 400 nm. The thickness of the TiO2 film is 4.0 μm.

[0130] The TiO2 film in this embodiment is grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0131] The titanium-tantalum (TiTa) alloy sheet with a bioactive TiO2 film on its surface in this embodiment has anatase TiO2 crystal phase composition, and tantalum oxide exists in an amorphous form. Immersion in simulated body fluid for 4 days can induce the formation of hydroxyapatite, thus proving that the modified titanium-tantalum alloy material in this embodiment has good bioactivity.

[0132] Comparative Example 1

[0133] To demonstrate the effect of low-temperature plasma treatment on modified titanium-tantalum alloy materials, a surface modification method without low-temperature plasma treatment was performed, including the following steps:

[0134] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 10%, and the balance is titanium (Ti) and other unavoidable impurities;

[0135] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O containing dissolved ammonium fluoride. The reactor is sealed and placed in an oven for hydrothermal reaction at 180°C for 30 hours. The mixed solution contains: ammonium fluoride at a concentration of 60 mmol / L, hydrogen peroxide at a volume percentage of 50%, isopropanol at a volume percentage of 20%, and the remainder is H2O. The reactor is 40% filled.

[0136] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and soak it in an alkaline solution for 48 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Let it air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a sodium hydroxide (NaOH) solution with a sodium hydroxide (NaOH) concentration of 1 mol / L.

[0137] According to the measurements, the TiTa alloy substrate / TiO2 film with no residual fluoride ions on the surface in this comparative example consists of a TiTa alloy substrate and a TiO2 film attached to the surface of the TiTa alloy substrate. The TiO2 film consists of particles with an average particle size of 2 μm. Each particle is self-assembled from multiple TiO2 single crystals with exposed (001) crystal planes. The TiO2 single crystal has a truncated octahedral configuration and is surrounded by eight isosceles trapezoidal (101) crystal planes and two square (001) crystal planes. The side length of the (001) crystal plane is 100 nm. The thickness of the TiO2 film is 2 μm.

[0138] The TiO2 film in this comparative embodiment was grown in situ on the surface of a titanium-tantalum (TiTa) alloy substrate. It has a very strong bond with the substrate material. Even after long-term (15 min) ultrasonic oscillation under high-power (100W) ultrasonic action, no detachment or peeling was observed, which fully ensures the structural stability of the TiO2 film as a transition layer.

[0139] The titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on its surface in this comparative embodiment has an anatase TiO2 crystalline phase composition, with tantalum oxide existing in an amorphous form. Immersion in simulated body fluid for more than 14 days is required to induce hydroxyapatite formation, demonstrating that the titanium-tantalum (TiTa) alloy substrate / TiO2 film with no residual fluoride ions on its surface in this embodiment possesses certain bioactivity. However, compared to the modified titanium-tantalum alloy material treated with low-temperature plasma, its bioactivity is lower, thus proving that low-temperature plasma treatment can effectively improve the bioactivity of the titanium-tantalum (TiTa) alloy substrate / TiO2 film.

[0140] Comparative Example 2

[0141] To demonstrate the effect of different fluorine source treatments on modified titanium-tantalum alloy materials, a surface modification method based on hydrofluoric acid (HF) treatment was conducted, including the following steps:

[0142] S1. Polish a titanium-tantalum (TiTa) alloy substrate with physical dimensions of 10mm×10mm×1mm sequentially with 150#, 600# and 1000# sandpaper until it is bright; then place the polished titanium-tantalum (TiTa) alloy substrate in anhydrous ethanol for ultrasonic degreasing, then rinse with deionized water and air dry naturally; wherein, the mass percentage of tantalum (Ta) in the titanium-tantalum (TiTa) alloy substrate is 20%, and the balance is titanium (Ti) and other unavoidable impurities;

[0143] S2. The air-dried titanium-tantalum (TiTa) alloy substrate from S1 is placed in a hydrothermal reactor lined with polytetrafluoroethylene. The reactor contains a mixed solution of hydrogen peroxide, isopropanol, and H2O to dissolve hydrofluoric acid. The reactor is sealed and placed in an oven for hydrothermal reaction at 180°C for 72 hours. The mixed solution contains 100 mmol / L hydrofluoric acid, 40% hydrogen peroxide, 40% isopropanol, and the remainder is H2O. The reactor is 60% full.

[0144] S3. After the hydrothermal reaction in S2 is completed, remove the hydrothermal reactor from the oven and allow it to cool naturally. Then, remove the titanium-tantalum (TiTa) alloy substrate from the hydrothermal reactor and soak it in an alkaline solution for 48 hours to replace fluoride ions. After that, remove it and rinse it with deionized water until the pH of the washing solution is close to neutral. Let it air dry naturally to obtain a titanium-tantalum (TiTa) alloy substrate / TiO2 film with no fluoride ion residue on the surface. The alkaline solution is a sodium hydroxide (NaOH) solution with a sodium hydroxide (NaOH) concentration of 1 mol / L.

[0145] Measurements showed that the TiO2 film in this comparative example had very poor adhesion to the surface of the titanium-tantalum (TiTa) alloy substrate. After 5 minutes of vibration under low-power (20W) ultrasound, the TiO2 film completely detached, thus losing its functional property as a transition layer to induce the deposition of hydroxyapatite in body fluids.

[0146] In summary, the modified titanium-tantalum alloy material of this invention utilizes a titanium dioxide (TiO2) film deposited on a titanium-tantalum alloy substrate for biomedical applications. This TiO2 film possesses the ability to rapidly induce the precipitation of calcium and phosphorus ions in bodily fluids as calcium hydroxyphosphate salts under physiological conditions. By rapidly depositing hydroxyapatite on the surface of the titanium-tantalum alloy substrate to form a gradient interface structure of titanium-tantalum alloy-titanium dioxide-hydroxyapatite, a strong chemical bond can be effectively promoted between the implant material and human bone tissue, ensuring a good bonding effect and accelerating the healing process between the implant and the hard tissue, effectively shortening the patient's recovery time. Furthermore, the titanium-tantalum alloy substrate not only effectively reduces the elastic modulus of pure titanium but also overcomes the high cost of pure tantalum, while possessing advantages such as strong corrosion resistance and good biocompatibility.

[0147] The surface modification method of the modified titanium-tantalum alloy material of the present invention involves placing the titanium-tantalum alloy substrate in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol and water for hydrothermal reaction, followed by fluoride ion replacement in an alkaline solution to grow a titanium dioxide (TiO2) film in situ on the surface of the titanium-tantalum alloy substrate. This effectively ensures the bonding ability between the titanium dioxide (TiO2) film and the titanium-tantalum alloy substrate and the structural stability of the transition layer. Then, it is subjected to low-temperature plasma treatment in a mixed atmosphere of argon and oxygen to further increase the hydroxyl content on the surface of the titanium dioxide (TiO2) film, thereby effectively enhancing the induction ability of the modified titanium-tantalum alloy material, reducing the energy barrier required to overcome apatite nucleation, and possessing the advantages of simple surface modification process, easy industrial scale-up, and environmentally friendly and non-corrosive raw materials.

[0148] Because the modified titanium-tantalum alloy material has strong bioactivity and the ability to rapidly induce the precipitation of calcium and phosphorus ions in body fluids as hydroxyapatite, using the modified titanium-tantalum alloy material of this invention as a biomedical material can help it form a strong chemical bond with human bone tissue as an implant material, thereby effectively shortening the recovery time of patients. It has promotional application value in the field of biomedical nanomaterials technology.

[0149] The above embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention.

Claims

1. A method for surface modification of a modified titanium-tantalum alloy material, characterized in that, Includes the following steps: S1. A titanium-tantalum alloy matrix is ​​placed in a mixed solution containing ammonium fluoride, hydrogen peroxide, isopropanol, and water for a hydrothermal reaction. The concentration of ammonium fluoride in the mixed solution is 60 mmol / L to 100 mmol / L, the volume percentage of hydrogen peroxide in the mixed solution is 30% to 50%, and the volume percentage of isopropanol in the mixed solution is 20% to 40%. S2. The titanium-tantalum alloy matrix after hydrothermal reaction is immersed in an alkaline solution and washed to obtain an intermediate product. The alkaline solution is selected from sodium hydroxide (NaOH) solution and / or potassium hydroxide (KOH) solution, the concentration of alkali in the alkaline solution is 1mol / L~2mol / L, and the immersion time is 24h~48h. The washing is done by rinsing with deionized water until the pH value of the washing solution is close to neutral. S3. The intermediate product is subjected to low-temperature plasma treatment in a mixed atmosphere of argon (Ar) and oxygen (O2) to obtain a titanium-tantalum alloy with a bioactive titanium dioxide (TiO2) film attached to its surface; the titanium dioxide (TiO2) film is bioactive, and the thickness of the titanium dioxide (TiO2) film is between 2 μm and 4 μm; the titanium dioxide (TiO2) film is composed of particles with a particle size between 2 μm and 4 μm. Each particle is composed of multiple titanium dioxide (TiO2) single crystals with exposed (001) crystal faces that are self-assembled; the titanium dioxide (TiO2) single crystal has a truncated octahedral configuration, and the titanium dioxide (TiO2) single crystal is surrounded by eight isosceles trapezoidal (101) crystal faces and two square (001) crystal faces, with the side length of the (001) crystal faces being 100nm~400nm.

2. The surface modification method for the modified titanium-tantalum alloy material according to claim 1, characterized in that, The composition of the titanium-tantalum alloy matrix includes 10% to 30% tantalum (Ta) by mass percentage, with the balance being titanium and unavoidable impurities.

3. The surface modification method for the modified titanium-tantalum alloy material according to claim 1, characterized in that, In S1: Before the titanium-tantalum alloy substrate is placed in the mixed solution, a thin passivation film on the surface of the titanium-tantalum alloy substrate is removed. The temperature for the hydrothermal reaction is 180℃~200℃; The hydrothermal reaction time is 30h~72h.

4. The surface modification method for the modified titanium-tantalum alloy material according to claim 1, characterized in that, In S3: The volume percentage of oxygen in the mixed atmosphere is 8%~12%; The gas flow rate of the mixed atmosphere is 3 L / min to 6 L / min; The power for low-temperature plasma treatment is 100~300W; The duration of the treatment and / or low-temperature plasma treatment is 10 to 30 minutes.