3D printing titanium alloy composite coating material and preparation method and application thereof

Abstract

The invention discloses a 3D printing titanium alloy composite coating material and a preparation method and application thereof, and relates to the technical field of titanium alloy materials. The micro-arc oxidation ceramic coating is formed on the 3D printing titanium alloy matrix, and the Mn-MOF material grows in situ, so that the biocompatibility of the titanium alloy can be remarkably improved, the composite coating not only improves the surface roughness of the 3D printing titanium alloy matrix, but also effectively promotes cell proliferation and adhesion through introduction of Mn, and the surface roughness of the 3D printing titanium alloy matrix is improved. Therefore, the application potential of the titanium alloy in the biomedical field is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing titanium alloy materials, and in particular to a 3D printing titanium alloy composite coating material and a preparation method and application thereof. Background Art

[0002] With the continuous development of science and technology, the emergence of 3D printing technology has brought revolutionary changes to the preparation of personalized medical devices and medical bone implant materials. Among them, TC4 titanium alloy has become one of the important materials in the field of medical 3D printing with its excellent corrosion resistance and mechanical strength. However, due to the particularity of the 3D printing method, the bone implant materials prepared by it still face important challenges. During the preparation process, the molten particles deposited on the surface of the material and the release of Al and V ions will seriously reduce the biocompatibility of the material. At the same time, the inherent biological inertness of titanium alloys and the lack of bone integration and bone induction properties make it difficult for titanium implants printed by different printing technologies to achieve good bone contact. In order to solve these problems, many scholars have prepared bioactive coatings on the surface of titanium alloys to improve the adhesion of cells to promote the interaction and bonding between implants and bone tissue.

[0003] The existing technology mainly adopts surface coating modification methods, such as micro-arc oxidation (MAO), multi-arc ion plating, hot dip, laser cladding technology, etc. At present, the coatings that improve the compatibility of titanium alloys in patents mostly adopt deposition methods. In recent years, micro-arc oxidation treatment has gradually become an important means of surface modification of titanium alloys. It can effectively improve the biocompatibility of titanium alloys by doping with bioactive elements. However, these doped ions will be unevenly distributed during the MAO process, resulting in toxicity, and the unstable release also reduces the biocompatibility of the material.

[0004] Therefore, there is an urgent need to improve the preparation method of titanium alloy coatings, to improve biocompatibility while reducing the risk of harmful ion release, and to improve the biosafety and stability of the coatings.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The purpose of the present invention is to provide a 3D printed titanium alloy composite coating material and a preparation method and application thereof, aiming to improve the biocompatibility of titanium alloy.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a 3D printed titanium alloy composite coating material, comprising a 3D printed titanium alloy substrate, a micro-arc oxidation ceramic coating attached to the 3D printed titanium alloy substrate, and a Mn-MOF material grown on the micro-arc oxidation ceramic coating.

[0009] In an alternative embodiment, the micro-arc oxidation ceramic coating is a silicon oxide coating or a hydroxyapatite coating;

[0010] and / or, the thickness of the 3D printed titanium alloy substrate is 2 mm - 3 mm, and the thickness of the micro-arc oxidation ceramic coating is 20 μm - 30 μm;

[0011] and / or, in the 3D printed titanium alloy composite coating material, the mass fraction of the Mn-MOF material is 5% - 15%.

[0012] Second, the present invention provides a method for preparing a 3D printed titanium alloy composite coating material according to any one of the foregoing embodiments, including: performing micro-arc oxidation treatment on a 3D printed titanium alloy substrate to form a micro-arc oxidation ceramic coating;

[0013] Mixing and reacting the titanium alloy material with a micro-arc oxidation layer with a Mn-MOF reaction solution.

[0014] In an alternative embodiment, the process of forming the micro-arc oxidation ceramic coating includes: using the 3D printed titanium alloy substrate as the anode and placing it in an electrolyte for micro-arc oxidation treatment;

[0015] wherein, the electrolyte includes: 15 g / L - 20 g / L of NaSiO3·9H2O, 2 g / L - 6 g / L of NaOH, 0.5 g / L - 5 g / L of KF·2H2O, and 3 mL / L - 7 mL / L of triethanolamine;

[0016] or, the electrolyte includes: 4 g / L - 7 g / L of sodium glycerophosphate and 25 g / L - 35 g / L of calcium acetate.

[0017] In an alternative embodiment, during the micro-arc oxidation treatment, a constant current power supply is used and the current density is controlled to be 1.0 A / dm 2 - 1.5 A / dm 2 , the frequency is 400 Hz - 600 Hz, and the treatment time is 5 min - 10 min.

[0018] In an alternative embodiment, the titanium alloy material with a micro-arc oxidation ceramic coating is subjected to a high-temperature reaction with a Mn-MOF reaction solution, and the reaction temperature is controlled to be 140 °C - 180 °C, and the reaction time is 10 h - 15 h.

[0019] In an alternative embodiment, the process of preparing the Mn-MOF reaction solution includes: mixing a manganese source solution and a ligand solution, performing a solvothermal reaction, controlling the reaction temperature to be 150 °C - 200 °C, and the reaction time to be 10 h - 15 h.

[0020] In an alternative embodiment, the molar ratio of manganese in the manganese source solution to the ligand in the ligand solution is adjusted to be (1.0 - 2.5):1;

[0021] And / or, the manganese source is selected from at least one of manganese nitrate, manganese acetate and manganese chloride, and the concentration of the manganese source solution is 0.02 mol / L - 0.08 mol / L;

[0022] And / or, the ligand is selected from at least one of trimesic acid, terephthalic acid and dimethylimidazole; the concentration of the ligand solution is 0.01 mol / L - 0.05 mol / L.

[0023] In an alternative embodiment, after the reaction with the Mn-MOF reaction solution is completed, the material is taken out for washing and drying; wherein, the drying temperature is controlled to be 40°C - 80°C.

[0024] In a third aspect, the present invention provides the use of the 3D printing titanium alloy composite coating material in any of the foregoing embodiments or the 3D printing titanium alloy composite coating material prepared by the preparation method in any of the foregoing embodiments in the 3D printing of bone implant materials.

[0025] The present invention has the following beneficial effects: By forming a micro-arc oxidation ceramic coating on the 3D printed titanium alloy substrate and in-situ growing Mn-MOF material, the biocompatibility of the 3D printed titanium alloy can be significantly improved. This composite coating not only increases the surface roughness of the 3D printed titanium alloy substrate, but also effectively promotes cell proliferation and adhesion through the introduction of Mn, thereby enhancing the application potential of titanium alloy in the field of biomedicine. Description of the Drawings

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can also be obtained based on these drawings without creative efforts.

[0027] Figure 1 SEM photograph of MAO-TC4 prepared for Comparative Example 1;

[0028] Figure 2 SEM photograph of Mn-MOF / MAO-TC4 prepared for Example 2;

[0029] Figure 3 SEM photograph of Mn-MOF / MAO-TC4 prepared for Example 3;

[0030] Figure 4 SEM photograph of MAO-TC4 prepared for Comparative Example 2;

[0031] Figure 5Scanning electron microscope photograph of Mn-MOF / MAO-TC4 prepared in Example 7;

[0032] Figure 6 Scanning electron microscope photograph of Mn-MOF / MAO-TC4 prepared in Example 8. Specific embodiments

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are followed. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0034] The embodiments of the present invention provide a preparation method for a 3D printing titanium alloy composite coating material. By micro-arc oxidation treatment combined with Mn-MOF materials, the biocompatibility of titanium alloys is significantly improved. The preparation steps are as follows:

[0035] S1. Micro-arc oxidation treatment

[0036] The 3D printing titanium alloy substrate is subjected to micro-arc oxidation treatment to form a micro-arc oxidation ceramic coating (i.e., MAO coating). By applying a high voltage on the surface of the 3D printing titanium alloy substrate, a ceramicized oxide film is generated in the electrolyte, which can significantly improve the wear resistance, corrosion resistance, and biocompatibility of the titanium alloy.

[0037] To further optimize the bonding strength between the MAO coating and the 3D printing titanium alloy substrate, reduce the porosity of the MAO coating and at the same time reduce the risk of harmful ion release, and improve the biological safety and stability of the coating, the inventors optimized the composition of the electrolyte, current density, frequency, treatment time, etc.:

[0038] In some embodiments, the process of forming the micro-arc oxidation ceramic coating includes: using the 3D printing titanium alloy substrate as the anode (the cathode is not limited, such as it can be a stainless steel plate), and placing it in the electrolyte for micro-arc oxidation treatment. The composition of the electrolyte can adopt the following two schemes:

[0039] Scheme 1: The electrolyte includes: 15 g / L - 20 g / L of NaSiO3·9H2O, 2 g / L - 6 g / L of NaOH, 0.5 g / L - 5 g / L of KF·2H2O, and 3 mL / L - 7 mL / L of triethanolamine. Using this electrolyte, a silicon oxide layer can be formed. Adding KF can increase the conductivity coefficient, and adding triethanolamine can improve the density of the coating. Specifically, the solvent of the electrolyte can be water. The concentration of NaSiO3·9H2O can be 15 g / L, 16 g / L, 17 g / L, 18 g / L, 18.6 g / L, 19 g / L, 20 g / L, etc.; the concentration of NaOH can be 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, etc.; the concentration of KF·2H2O (potassium fluoride dihydrate) can be 0.5 g / L, 1.0 g / L, 2.0 g / L, 3.0 g / L, 4.0 g / L, 5.0 g / L, etc.; the concentration of triethanolamine can be 3 mL / L, 4 mL / L, 5 mL / L, 6 mL / L, 7 mL / L, etc.

[0040] Scheme 2: The electrolyte includes: 4 g / L - 7 g / L of sodium glycerophosphate and 25 g / L - 35 g / L of calcium acetate. The formed coating is hydroxyapatite. When the sodium glycerophosphate and calcium acetate solutions are mixed, the glycerophosphate ions in the solution will react with Ca 2 + to generate water-insoluble hydroxyapatite precipitate. Specifically, the solvent of the electrolyte can be water. The concentration of sodium glycerophosphate can be 4 g / L, 5 g / L, 5.36 g / L, 6 g / L, 7 g / L, etc.; the concentration of calcium acetate can be 25 g / L, 28 g / L, 30 g / L, 31.62 g / L, 32 g / L, 35 g / L, etc.

[0041] In some embodiments, during the micro-arc oxidation process, a constant current power supply is used to perform micro-arc oxidation on the 3D printed titanium alloy substrate, and the current density is controlled to be 1.0 A / dm 2 - 1.5 A / dm 2 , the frequency is 400 Hz - 600 Hz, and the treatment time is 5 min - 10 min. By regulating the parameters of the power supply, the optimized MAO coating exhibits lower porosity, ensuring a lower risk of harmful ion release, thereby improving the biosecurity and stability of the coating. If the current density is too large, the energy of spark discharge during oxidation will increase, the formed discharge channel will become larger, and the generated ceramic particles and pores will also be larger, resulting in an increase in the porosity of the coating and an increase in the risk of harmful ion release; if the current density is too small, the growth rate of the ceramic film will decrease, the film layer will be thinner, it is difficult to form a coating, the coating uniformity will be reduced, and at the same time, the bonding strength between the coating and the substrate will be reduced, and the coating is likely to fall off.

[0042] Specifically, the current density can be 1.0 A / dm2 、1.1 A / dm 2 、1.2 A / dm 2 、1.3 A / dm 2 、1.4 A / dm 2 、1.5 A / dm 2 etc.; the frequency can be 400 Hz, 450 Hz, 500 Hz, 550 Hz, 600 Hz, etc.; the processing time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, etc.

[0043] It should be noted that by adopting a specific electrolyte formula and reaction conditions, the uniform growth of the Mn-MOF coating on the surface of the micro-arc oxidation layer is ensured, and the problems of non-uniformity and local toxicity are avoided.

[0044] S2. Provide the Mn-MOF reaction solution

[0045] The process of preparing the Mn-MOF reaction solution includes: mixing the manganese source solution and the ligand solution, and carrying out a solvothermal reaction. The manganese source solution and the ligand solution can adopt the reaction solutions commonly used for preparing Mn-MOF, and the specific types of the manganese source and the ligand are not limited.

[0046] In some embodiments, the reaction temperature of the solvothermal reaction is controlled at 150°C - 200°C, such as it can be 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, etc.; the reaction time is 10 h - 15 h, such as it can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, etc. The reaction process can be carried out in a high-pressure reaction kettle with a Teflon liner, and it is appropriate to control the reaction temperature and time within the above ranges to form a uniform Mn-MOF material.

[0047] Furthermore, the solvents for preparing the manganese source solution and the ligand solution are not limited, such as it can be anhydrous ethanol. The manganese source and the solvent are magnetically stirred at room temperature (such as 25°C) for 10 min - 30 min to obtain the manganese source solution. The ligand and the solvent are magnetically stirred at room temperature (such as 25°C) for 10 min - 30 min to obtain the ligand solution.

[0048] Furthermore, the molar ratio of manganese in the manganese source solution to the ligand in the ligand solution is regulated to be (1.0 - 2.5):1. By regulating the molar ratio of manganese to the ligand within the above range, the structure of the formed Mn-MOF material can be regulated, which is conducive to in-situ growth on the titanium alloy material. Specifically, the molar ratio of manganese to the ligand can be 1.0:1, 1.3:1, 1.5:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, etc.

[0049] Further, the manganese source is selected from at least one of manganese nitrate, manganese acetate, and manganese chloride, and the manganese source can be any one or several of the above. The concentration of the manganese source solution is 0.02 mol / L - 0.08 mol / L, such as 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, etc.

[0050] Further, the ligand is selected from at least one of trimesic acid (BTC), terephthalic acid, and dimethylimidazole, and the ligand can be any one or several of the above. The concentration of the ligand solution is 0.01 mol / L - 0.05 mol / L, such as 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, etc.

[0051] S3. In-situ growth

[0052] Mix the 3D printed titanium alloy material with a micro-arc oxidation ceramic coating with the Mn-MOF reaction solution and react. Under high-temperature conditions, Mn-MOF grows in-situ on the material surface. The introduction of Mn effectively promotes cell proliferation and adhesion, thereby improving the application potential of 3D printed titanium alloy in the field of biomedical applications.

[0053] In some embodiments, the 3D printed titanium alloy material with a micro-arc oxidation ceramic coating is subjected to a high-temperature reaction with the Mn-MOF reaction solution, and the reaction temperature is controlled to be 140°C - 180°C, and the reaction time is 10 h - 15 h. The reaction temperature and time are preferably within the above ranges to enable the uniform growth of the Mn-MOF material. Specifically, the reaction temperature can be 140°C, 150°C, 160°C, 170°C, 180°C, etc.; the reaction time can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, etc., and the reaction process can be carried out in a high-pressure reactor.

[0054] Experimental results show that the Mn-MOF / MAO composite coating provided by the embodiments of the present invention has a uniform surface and no obvious defects, significantly improving the stability and biocompatibility of the coating, and providing an excellent performance basis for the application of 3D printed titanium alloy in biomedical fields such as orthopedic implants.

[0055] S4. Post-treatment

[0056] After the reaction with the Mn-MOF reaction solution is completed, take out the material for washing and drying to remove unreacted impurities on the surface.

[0057] Specifically, the washing method is not limited, and distilled water can be used for water washing.

[0058] Further, the drying temperature can be 40°C - 80°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, etc., and it can be carried out in a vacuum drying oven.

[0059] The embodiment of the present invention provides a 3D printed titanium alloy composite coating material, which includes a 3D printed titanium alloy matrix, on which a micro-arc oxidation ceramic coating is attached, and a Mn-MOF material grows on the micro-arc oxidation ceramic coating. The composite coating not only improves the surface roughness of the 3D printed titanium alloy matrix, but also effectively promotes cell proliferation and adhesion through the introduction of Mn, thereby improving the application potential of titanium alloy in the biomedical field. The titanium alloy composite material provided by the embodiment of the present invention can be prepared into an osteoplasty implant material by 3D printing technology.

[0060] In some embodiments, the micro-arc oxidation ceramic coating is a silicon oxide coating or a hydroxyapatite coating, and the reaction products are different according to different electrolytes. The thickness of the 3D printed titanium alloy matrix is 2mm - 3mm (such as 2.0mm, 2.5mm, 3.0mm, etc.), and the thickness of the micro-arc oxidation ceramic coating is 20μm - 30μm (such as 20μm, 25μm, 30μm, etc.).

[0061] Further, in the 3D printed titanium alloy composite coating material, the mass fraction of the Mn-MOF material is 5% - 15%, such as 5%, 8%, 10%, 12%, 15%, etc. The preparation fraction of the Mn-MOF material is preferably within the above range to further promote the effect of cell proliferation and adhesion.

[0062] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0063] Comparative Example 1

[0064] Using a 3D printed TC4 titanium alloy with a thickness of 2mm as the anode and a stainless steel metal plate as the cathode, an electrolyte composed of 5.36g / L of sodium glycerophosphate and 31.62g / L of calcium acetate, and constant current MAO for 8 minutes was carried out at a current density of 1.2A / dm 2 and a frequency of 500Hz. The obtained sample was washed with distilled water in an ultrasonic cleaner and dried to obtain the product MAO-TC4.

[0065] Among them, the scanning electron microscope photo of the obtained MAO-TC4 is shown in Figure 1 , and it can be seen that the holes on the coating surface are evenly distributed and the pore diameter is relatively large.

[0066] Example 1

[0067] This embodiment provides a preparation method of a titanium alloy composite material, and the steps are as follows:

[0068] (1) Micro-arc oxidation treatment

[0069] The specific steps refer to Comparative Example 1.

[0070] (2) Provide Mn-MOF reaction solution

[0071] Take 0.223 g of manganese nitrate tetrahydrate and add it to 20 mL of absolute ethanol. After complete dissolution, solution A is obtained. Take 0.115 g of trimesic acid and add it to 20 mL of absolute ethanol. After complete dissolution, solution B is obtained. Mix solution A and solution B and stir them on a magnetic stirrer for 20 min. Then, react them in a Teflon-lined autoclave (50 mL) at a temperature of 170 °C for 12 h to obtain the Mn-MOF reaction solution.

[0072] (3) In-situ growth

[0073] Put the obtained Mn-MOF reaction solution and MAO-TC4 into an autoclave and react. The reaction temperature is 150 °C and the time is 12 h.

[0074] (4) Post-treatment

[0075] Wash the reacted titanium alloy with distilled water and dry it (60 °C, 12 h, the same below). The final sample is Mn-MOF / MAO-TC4.

[0076] The results show that the pores on the surface of the coating are of different sizes and the surface is rough. The results of CCK-8 assay for the activity of rat bone marrow mesenchymal stem cells show that compared with the micro-arc oxidation coating in Comparative Example 1, the cell activity of the composite coating is increased by 11%.

[0077] The method for CCK-8 assay of the activity of rat bone marrow mesenchymal stem cells is as follows:

[0078] For the cell compatibility test of the coating, place the titanium alloy samples of each group after high-temperature sterilization in a 24-well plate. Inoculate BMSCs cells on the samples of each group at a concentration of 1×10 4 cells / mL. After culturing for 1 d, 3 d, and 5 d, take out the samples, add 10% CCK-8 solution (volume fraction), and incubate them in a cell culture incubator (5% CO2, 37 °C) for 2 h. Measure the absorbance values (O.D.) of the experimental group and the control group at 450 nm with an enzyme-linked immunosorbent assay reader, and determine their relative growth rate (RGR) through formula (1).

[0079]

[0080] In the formula, As is the O.D. value of the experimental group, Ac is the O.D. value of the control group, and Ab is the O.D. value of the blank control group.

[0081] Example 2

[0082] The difference from Example 1 is only that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 160 °C, and other reaction conditions and material compositions remain unchanged.

[0083] The results show that: the scanning electron microscope photograph of the obtained Mn-MOF / MAO-TC4 is shown in Figure 2 , and its coating surface is large and the distribution of the Mn-MOF material is uneven.

[0084] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 1, the cell activity of the composite coating is increased by 25%.

[0085] Example 3

[0086] The difference from Example 1 is only that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 170 °C, and other reaction conditions and material compositions remain unchanged.

[0087] The results show that: the scanning electron microscope photograph of the obtained Mn-MOF / MAO-TC4 is shown in Figure 3 , and it can be seen that the coating surface of the coating has large holes and the Mn-MOF adheres more densely, forming a relatively rough surface.

[0088] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 1, the cell activity of the composite coating is increased by 19%.

[0089] Example 4

[0090] The difference from Example 1 is only that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 180 °C, and other reaction conditions and material compositions remain unchanged.

[0091] The results show that: for Mn-MOF / MAO-TC4 obtained, its coating surface has large holes and the most significant irregular roughness.

[0092] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 1, the cell activity of the composite coating is increased by 7%.

[0093] Comparative Example 2

[0094] Using a 3D printed TC4 titanium alloy with a thickness of 2 mm as the anode and a stainless steel metal plate as the cathode, an electrolyte composed of 18.6 g / L of NaSiO3·9H2O, 4 g / L of NaOH, 2 g / L of KF·2H2O, and 5 mL / L of triethanolamine, at 1.2 A / dm 2Under the conditions of a current density of [current density value] and a frequency of 500 Hz, micro-arc oxidation was carried out under constant current for 8 minutes. After washing the obtained specimen with distilled water in an ultrasonic cleaner and drying it, the product MAO-TC4 was obtained.

[0095] The scanning electron microscope photograph of MAO-TC4 prepared in this comparative example is shown in Figure 4 , and it can be seen that the surface of the coating has a spongy porous structure with uniform distribution.

[0096] The results of CCK-8 rat bone marrow mesenchymal stem cell activity detection show that compared with the micro-arc oxidation coating in Comparative Example 1, the cell activity of the coating has increased by 26%.

[0097] Example 5

[0098] This example provides a preparation method of a titanium alloy composite material, and the steps are as follows:

[0099] (1) Micro-arc oxidation treatment

[0100] For the specific steps, refer to Comparative Example 2.

[0101] (2) Provide Mn-MOF reaction solution

[0102] Take 0.223 g of manganese nitrate tetrahydrate and add it to 20 mL of absolute ethanol. After fully dissolving, solution A is obtained. Take 0.115 g of trimesic acid and add it to 20 mL of absolute ethanol. After complete dissolution, solution B is obtained. Mix solution A and solution B and stir for 20 minutes on a magnetic stirrer, and then react in a polytetrafluoroethylene-lined autoclave (50 ml) at a temperature of 170 °C for 12 hours to obtain the Mn-MOF reaction solution.

[0103] (3) In-situ growth

[0104] Put the obtained Mn-MOF reaction solution and MAO-TC4 into an autoclave to react. The reaction temperature is 140 °C and the time is 12 hours.

[0105] (4) Post-treatment

[0106] Wash the reacted titanium alloy with distilled water and dry it. The final specimen is Mn-MOF / MAO-TC4.

[0107] The results show that the pores on the surface of its coating are unevenly distributed, the pore sizes are different, and the surface roughness is relatively high.

[0108] The results of CCK-8 rat bone marrow mesenchymal stem cell activity detection show that compared with the micro-arc oxidation coating in Comparative Example 2, the cell activity of the composite coating has increased by 29%.

[0109] Example 6

[0110] It is only different from Example 5 in that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 150 °C, and other reaction conditions and material compositions remain unchanged.

[0111] The results show that: for the obtained Mn-MOF / MAO-TC4, the pores on the coating surface are filled with granular substances, and the distribution is relatively uniform, and the surface roughness is relatively high.

[0112] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 2, the cell activity of the composite coating has increased by 45%.

[0113] Example 7

[0114] It is only different from Example 5 in that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 160 °C, and other reaction conditions and material compositions remain unchanged.

[0115] The results show that: the scanning electron microscope photo of the obtained Mn-MOF / MAO-TC4 is shown in Figure 5 , the pores on the coating surface are filled with granular substances, and the distribution is relatively uniform, and the surface roughness is relatively high.

[0116] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 2, the cell activity of the composite coating has increased by 58%.

[0117] Example 8

[0118] It is only different from Example 5 in that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 170 °C, and other reaction conditions and material compositions remain unchanged.

[0119] The results show that: the scanning electron microscope photo of the obtained Mn-MOF / MAO-TC4 is shown in Figure 6 , obvious particle filling phenomenon appears on the coating surface, and the particle distribution is relatively concentrated.

[0120] The CCK-8 rat bone marrow mesenchymal stem cell activity detection results show that, compared with the micro-arc oxidation coating of Comparative Example 2, the cell activity of the composite coating has increased by 37%.

[0121] Example 9

[0122] It is only different from Example 5 in that: in step (3), the high-temperature reaction temperature of the Mn-MOF reaction solution and MAO-TC4 is 180 °C, and other reaction conditions and material compositions remain unchanged.

[0123] The results show that for the obtained Mn-MOF / MAO-TC4, obvious particle accumulation appears on the coating surface, and the particles are concentrated in distribution to form a particle layer.

[0124] The results of CCK-8 detection of the activity of rat bone marrow mesenchymal stem cells show that, compared with the micro-arc oxidation coating in Comparative Example 2, the cell activity of the composite coating is increased by 17%.

[0125] Example 10

[0126] The difference from Example 5 is only that: the current density in step (1) is 1.0 A / dm 2 .

[0127] The results show that: the sponge-like porous structure on the coating surface has relatively large holes, and the Mn-MOF materials are unevenly distributed.

[0128] The results of CCK-8 detection of the activity of rat bone marrow mesenchymal stem cells show that, compared with the micro-arc oxidation coating in Comparative Example 2, the cell activity of the coating is increased by 15%.

[0129] Example 11

[0130] The difference from Example 5 is only that: the current density in step (1) is 1.3 A / dm 2 .

[0131] The results show that: the sponge-like porous structure on the coating surface has more cracks, and no Mn-MOF material adheres to the cracks.

[0132] The results of CCK-8 detection of the activity of rat bone marrow mesenchymal stem cells show that, compared with the micro-arc oxidation coating in Comparative Example 2, the cell activity of the coating is increased by 24%.

[0133] Example 12

[0134] The difference from Example 5 is only that: the current density in step (1) is 1.5 A / dm 2 .

[0135] The results show that: the sponge-like porous structure on the coating surface has a large number of cracks, and no Mn-MOF material adheres to the cracks.

[0136] The results of CCK-8 detection of the activity of rat bone marrow mesenchymal stem cells show that, compared with the micro-arc oxidation coating in Comparative Example 2, the cell activity of the coating is increased by 13%.

[0137] Example 13

[0138] The difference from Example 5 is only that: the reaction time in step (2) is 14 h.

[0139] The results show that the coating surface has a spongy porous structure, but the Mn-MOF material is densely distributed and the particles are concentrated.

[0140] The results of CCK-8 assay for the activity of rat bone marrow mesenchymal stem cells showed that the cell activity of the composite coating was increased by 14% compared with that of the micro-arc oxidation coating in Comparative Example 2.

[0141] Example 14

[0142] The difference from Example 5 is only that: the reaction time in step (2) is 10 h.

[0143] The results show that the coating surface has a spongy porous structure, but the Mn-MOF material is unevenly distributed and the particle coverage is less.

[0144] The results of CCK-8 assay for the activity of rat bone marrow mesenchymal stem cells showed that the cell activity of the composite coating was increased by 10% compared with that of the micro-arc oxidation coating in Comparative Example 2.

[0145] Comparative Example 3

[0146] The difference from Example 5 is only that: the manganese source in step (2) is manganese chloride tetrahydrate (controlling the molar amount of manganese to be the same as that in Example 5).

[0147] The results show that the coating surface has a spongy porous structure, but the Mn-MOF material adheres less and the particles are irregular flakes.

[0148] The results of CCK-8 assay for the activity of rat bone marrow mesenchymal stem cells showed that the cell activity of the composite coating was increased by 5% compared with that of the micro-arc oxidation coating in Comparative Example 2.

[0149] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A 3D printed titanium alloy composite coating material, characterized in that: It comprises a 3D printed titanium alloy substrate, a micro-arc oxidation ceramic coating is attached to the 3D printed titanium alloy substrate, and a Mn-MOF material is grown on the micro-arc oxidation ceramic coating.

2. The 3D printing titanium alloy composite coating material according to claim 1, characterized in that: The micro-arc oxidation ceramic coating is a silicon oxide coating or a hydroxyapatite coating; And / or, the thickness of the 3D printed titanium alloy substrate is 2 mm-3 mm, and the thickness of the micro-arc oxidation ceramic coating is 20 μm-30 μm; And / or, in the 3D printing titanium alloy composite coating material, the mass fraction of the Mn-MOF material is 5%-15%.

3. A method for preparing a 3D printed titanium alloy composite coating material according to any one of claims 1 to 2, characterized in that: include: Performing micro-arc oxidation treatment on the 3D printed titanium alloy substrate to form the micro-arc oxidation ceramic coating; The titanium alloy material having the micro-arc oxidation ceramic coating is mixed with the Mn-MOF reaction solution for reaction.

4. The preparation method according to claim 3, characterized in that: The process of forming the micro-arc oxidation ceramic coating includes: using a 3D printed titanium alloy substrate as an anode and placing it in an electrolyte for micro-arc oxidation treatment; Wherein, the electrolyte comprises: NaSiO3·9H2O 15g / L-20g / L, NaOH 2g / L-6g / L, KF·2H2O 0.5g / L-5g / L and triethanolamine 3mL / L-7mL / L; Alternatively, the electrolyte comprises: 4 g / L-7 g / L sodium glycerophosphate and 25 g / L-35 g / L calcium acetate.

5. The preparation method according to claim 4, characterized in that: During the micro-arc oxidation process, a constant current power supply was used and the current density was controlled to be 1.0 A / dm 2 -1.5A / dm 2 , frequency is 400Hz-600Hz, and processing time is 5min-10min.

6. The preparation method according to claim 3, characterized in that: The titanium alloy material with the micro-arc oxidation ceramic coating is subjected to a high-temperature reaction with the Mn-MOF reaction solution, the reaction temperature is controlled to be 140° C.-180° C., and the reaction time is 10 h-15 h.

7. The preparation method according to claim 3 or 6, characterized in that: The process of preparing the Mn-MOF reaction solution includes: mixing a manganese source solution and a ligand solution, performing a solvent thermal reaction, controlling the reaction temperature to be 150° C.-200° C., and the reaction time to be 10 h-15 h.

8. The preparation method according to claim 7, characterized in that: The molar ratio of manganese in the manganese source solution to the ligand in the ligand solution is regulated to be (1.0-2.5):1; And / or, the manganese source is selected from at least one of manganese nitrate, manganese acetate and manganese chloride, and the concentration of the manganese source solution is 0.02 mol / L-0.08 mol / L; And / or, the ligand is selected from at least one of trimesic acid, terephthalic acid and dimethylimidazole; the concentration of the ligand solution is 0.01 mol / L-0.05 mol / L.

9. The preparation method according to claim 4, characterized in that: After the reaction with the Mn-MOF reaction solution is completed, the material is taken out for washing and drying; wherein the drying temperature is controlled to be 40° C.-80° C.

10. Use of the 3D printed titanium alloy composite coating material according to any one of claims 1 to 2 or the 3D printed titanium alloy composite coating material prepared by the preparation method according to any one of claims 3 to 9 in 3D printing to prepare bone implant materials.

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