A surface structure modified bioceramic bone repair scaffold and a preparation method thereof

Abstract

The application discloses a surface structure modified bioceramic bone repair bracket and a preparation method thereof. The preparation method comprises the following steps: step S1: a mixture containing ceramic powder, photosensitive resin and dispersing agent is ball milled, printed, discharged, sintered 1, and a porous structure three-dimensional bracket is obtained; and step S2: the porous structure three-dimensional bracket is immersed in an immersion liquid, and a surface structure modified bioceramic bone repair bracket is obtained. The immersion liquid comprises a first layer of immersion liquid and a second layer of immersion liquid. The bioceramic bracket provided by the application has superhydrophilicity, high surface activity, and a fast fusion speed with bone tissue, is beneficial to osteogenesis and vascularization, and is a good bone repair material with biological activity.

Description

TECHNICAL FIELD

[0001] The application relates to a surface structure modified bioceramic bone repair scaffold and a preparation method thereof, and belongs to the technical field of bioceramic bone repair scaffolds. BACKGROUND

[0002] At present, the method of implanting artificial bones is very common in the treatment of bone defect patients. An ideal bone repair scaffold needs to have good biocompatibility, biodegradability, three-dimensional porous structure, stable mechanical strength, good hydrophilicity, high surface activity and the like.

[0003] Bioceramic scaffolds are widely used in bone tissue engineering due to their osteogenic chemical composition and material properties. Compared with the traditional pore-forming agent forming process, the bioceramic prepared by the three-dimensional printing technology has the natural advantages of controllable pore size and structure, and the mechanical strength of the bioceramic scaffold is stable.

[0004] A common problem of bioceramic scaffolds is that the ceramic surface structure is dense, the surface roughness and surface energy are low, the surface activity of the material is low, and the hydrophilicity is poor. The ceramic scaffold with high surface activity and hydrophilicity is more conducive to the infiltration of blood after implantation, can stabilize the blood clot, and is more conducive to osteogenesis; meanwhile, the scaffold material with a high active surface can rapidly release and exchange ions after implantation, which is beneficial to the loading of active factors, cell adhesion and growth, extracellular matrix deposition and vascular ingrowth, thereby promoting early osteogenesis. Therefore, developing a porous bioceramic scaffold with high surface activity and hydrophilicity has important value in the field of bone repair. SUMMARY

[0005] To solve the above problems, the application provides a preparation method of a surface structure modified bioceramic bone repair scaffold. The bioceramic bone repair scaffold prepared by surface structure modification has ultra-high hydrophilicity and surface activity, and the preparation method is simple and easy to operate.

[0006] According to one aspect of the application, a preparation method of a surface structure modified bioceramic bone repair scaffold is provided, and the preparation method comprises the following steps:

[0007] Step S1: ball milling, printing, gel removal and sintering 1 of a mixture containing ceramic powder, photosensitive resin and dispersant to obtain a three-dimensional scaffold with a porous structure;

[0008] Step S2: immersing the three-dimensional scaffold with a porous structure in an immersion liquid to obtain a surface structure modified bioceramic bone repair scaffold;

[0009] The immersion liquid comprises a first layer of immersion liquid and a second layer of immersion liquid.

[0010] The powder particle size D50 in the first layer impregnation solution is 20 ± 3 μm, and D90 is 30 ± 5 μm.

[0011] The powder particle size D50 in the second layer impregnation solution is 5 ± 2 μm, and D90 is 8 ± 2 μm.

[0012] Optionally, the impregnation solution comprises water, powder and dopamine.

[0013] Optionally, the powder is selected from at least one of bioactive glass, beta-tricalcium phosphate, alpha-tricalcium phosphate, xonotlite, hydroxyapatite, calcium silicate, hardystonite, and diopside.

[0014] Optionally, the concentration of dopamine in the impregnation solution is 2-8 g / L.

[0015] Optionally, the concentration of dopamine in the impregnation solution is independently selected from any value or a range between any two values of 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, and 8 g / L.

[0016] Optionally, the mass fraction of powder in the solution in the first layer impregnation solution is 15%-25%.

[0017] Optionally, the mass fraction of powder in the solution in the first layer impregnation solution is independently selected from any value or a range between any two values of 15%, 18%, 20%, 22%, and 25%.

[0018] Optionally, the mass fraction of powder in the solution in the second layer impregnation solution is 8-15%.

[0019] Optionally, the mass fraction of powder in the solution in the second layer impregnation solution is independently selected from any value or a range between any two values of 8%, 9%, 10%, 12%, and 15%.

[0020] Optionally, the preparation method of the impregnation solution comprises: mixing water and dopamine, stirring for 10 min-2 h, adding powder and mechanically stirring for 6-24 h to obtain the impregnation solution.

[0021] Optionally, after the water and dopamine are mixed, the pH value is adjusted to 7.5-9.0.

[0022] Optionally, in the step S2, the porous structure three-dimensional scaffold is immersed in the first layer impregnation solution for 1, dried for 1, immersed in the second layer impregnation solution for 2, dried for 2, and sintered for 2 to obtain the surface structure modified bioceramic bone repair scaffold.

[0023] Optionally, in the step S2, the temperature of the sintering 2 is 800-1000℃, and the time of the sintering 2 is 30-180 min.

[0024] Optionally, in the step S2, the temperature of the sintering 2 is independently selected from any value of 800℃, 850℃, 900℃, 950℃, 1000℃ or a range value between any two of the above.

[0025] Optionally, in the step S2, the time of the sintering 2 is independently selected from any value of 30 min, 60 min, 90 min, 120 min, 150 min, 180 min or a range value between any two of the above.

[0026] Optionally, the time of the impregnation 1, impregnation 2 is independently selected from 5-30 min.

[0027] Optionally, the temperature of the drying 1, drying 2 is independently selected from 40-90℃, and the time of the drying 1, drying 2 is independently selected from 1-5 h.

[0028] Optionally, in the step S1, the ceramic powder is selected from at least one of β-tricalcium phosphate, α-tricalcium phosphate, xonotlite, hydroxyapatite, calcium silicate, hardystonite, diopside.

[0029] Optionally, the photosensitive resin is selected from at least one of commercial photosensitive resin Ausbond A370 or Formlabs photosensitive resin.

[0030] Optionally, the dispersant is selected from at least one of propylene glycol methyl ether, BYK-111, Triton X-100, KH-550, KH-560.

[0031] Optionally, the mass ratio of the ceramic powder, photosensitive resin, dispersant is 1g: (0.3-0.5) g: (0.05-0.1) g.

[0032] Optionally, the time of the ball milling is 28-56 h.

[0033] Optionally, the printing manner is a three-dimensional printing technology, and the forming precision of the three-dimensional printing technology is 30-100 μm, wherein the pore size distribution of the scaffold is greater than 85% in the range of 50-800 μm.

[0034] Optionally, in the step S1, the temperature of the degassing is 400-700℃, and the time of the degassing is 180-300 min.

[0035] Optionally, in the step S1, the temperature of the sintering 1 is 1150-1450℃, and the time of the sintering 1 is 120-500 min.

[0036] According to still another aspect of the present application, there is provided a surface structure modified bioceramic bone repair scaffold prepared by the preparation method described above.

[0037] As an optional implementation, the present application is realized by the following technical solutions:

[0038] The preparation method of the surface structure modified bioceramic bone repair scaffold has the following steps:

[0039] (1) Preparation of a porous bioceramic scaffold: ceramic powder is uniformly mixed with a photosensitive resin dispersant, and a three-dimensional scaffold with a porous structure is obtained by three-dimensional printing technology and glue removal sintering;

[0040] (2) Surface modification: two layers of powder coatings are coated on the surface of the three-dimensional scaffold with a porous structure by a solution immersion method, and a surface structure modified bioceramic scaffold is obtained after sintering.

[0041] In step (2), the immersion process is as follows: first layer and second layer immersion solutions are respectively configured, the three-dimensional scaffold is first immersed in the first layer immersion solution, ultrasonic dispersion is performed for 5-30 min, the excess solution is shaken off, and after air drying or oven drying, the three-dimensional scaffold is placed in the second layer immersion solution, ultrasonic dispersion is performed for 5-30 min, the excess solution is shaken off, and after air drying or oven drying, a surface structure modified bioceramic scaffold is obtained after sintering.

[0042] The present application can produce the following beneficial effects:

[0043] 1) The porous bioceramic scaffold provided by the present application is obtained by three-dimensional printing process, and parts with complex structure, precise structure, high porosity and good pore connectivity can be prepared.

[0044] 2) The surface structure modified bioceramic bone repair scaffold provided by the present application is modified in structure on the surface of the three-dimensional scaffold with a porous structure by a solution immersion method. Compared with the traditional bioceramic scaffold with a dense surface structure, the present application increases the surface roughness of the material and improves the surface energy of the material by two layers of immersion, i.e., large particle size in the first layer of immersion and small particle size in the second layer of immersion. The sintering temperature after immersion is controlled to make the material have superhydrophilicity and surface activity, which is conducive to stabilizing blood clots, promoting cell adhesion and growth, accelerating interface ion exchange, promoting extracellular matrix deposition and vascular ingrowth, thereby promoting early osteogenesis. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The pore size range and distribution diagram of the three-dimensional printed porous scaffold of the present application;

[0046] Figure 2 The structural diagram of the three-dimensional printed porous scaffold of the present application;

[0047] Figure 3 Pore size range and distribution map of the three-dimensional printed porous scaffold with surface structure modification of the application;

[0048] Figure 4 Structure diagram of the three-dimensional printed porous scaffold with surface structure modification of the application;

[0049] Figure 5 Surface morphology (500 times magnification) of the three-dimensional printed porous scaffold (a1), surface morphology (5000 times magnification) of the three-dimensional printed porous scaffold (a2), surface morphology (500 times magnification) of the three-dimensional printed porous scaffold after surface modification (b1), surface morphology (5000 times magnification) of the three-dimensional printed porous scaffold after surface modification (b2) of the application;

[0050] Figure 6 Cell proliferation rate data of the application. DETAILED DESCRIPTION

[0051] The application will be described in detail below with reference to the examples, but the application is not limited to these examples.

[0052] Unless otherwise specified, the raw materials and reagents in the examples of the application are purchased through commercial channels.

[0053] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. In the quantitative tests in the following examples, three repeated experiments were set up, and the average value was taken as the result.

[0054] Example 1

[0055] Preparation of the wollastonite bioceramic porous scaffold:

[0056] (1) 20 g of photosensitive resin Ausbonds A370 and 3 g of dispersant propylene glycol methyl ether were weighed and mixed, placed in a ball mill tank containing zirconia grinding balls, 50 g of wollastonite powder was added to the ball mill tank, and the mixture was ball milled for 40 h; the obtained slurry was placed in the slurry tank of a DLP photocuring three-dimensional printer, and was printed according to the pre-set pattern, with a layer thickness of 50 μm, and was placed in anhydrous ethanol for cleaning to remove the un-solidified slurry to obtain a bioceramic porous scaffold green body.

[0057] (2) The bioceramic porous scaffold green body was degassed at 500 ℃ for 3 h and sintered at 1300 ℃ for 3 h, and finally a wollastonite bioceramic porous scaffold was obtained.

[0058] Example 2

[0059] Surface structure modification of the bioceramic porous scaffold:

[0060] (1) The first layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 8.5, mechanical stirring for 2 h, 90 g of β-tricalcium phosphate powder was added, and the stirring was continued for 20 h. The particle size of the β-tricalcium phosphate powder was D50 = 19.8 μm, and D90 = 31.1 μm.

[0061] (2) The second layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 8.5, mechanical stirring for 2 h, 50 g of bioactive glass powder was added, and the stirring was continued for 20 h. The particle size of the bioactive glass powder 45S5 was D50 = 4.5 μm, and D90 = 8.6 μm.

[0062] (3) The 10 three-dimensional scaffolds obtained in Example 1 were first immersed in the first layer of impregnation solution, ultrasonic dispersion for 30 min, and the excess solution was shaken off. The dried scaffolds were immersed in the second layer of impregnation solution, ultrasonic dispersion for 10 min, and the excess solution was shaken off. The dried scaffolds were sintered at a temperature of 950 ℃ for 60 min, and the surface structure modified bioceramic porous scaffold was obtained.

[0063] Example 3

[0064] Preparation of xonotlite bioceramic porous scaffold:

[0065] (1) 20 g of photosensitive resin Ausbonds A370 and 3 g of dispersant propylene glycol methyl ether were weighed and mixed in a ball mill tank containing zirconia grinding balls. 50 g of β-tricalcium phosphate powder was added to the ball mill tank, and the mixture was ball milled for 28 h. The mixed slurry was placed in the slurry tank of a DLP light curing three-dimensional printer, and was printed according to the pre-set pattern with a layer thickness of 30 μm. The scaffold was cleaned in anhydrous ethanol to remove the un-solidified slurry and obtain the green body of the bioceramic porous scaffold.

[0066] (2) The green body of the bioceramic porous scaffold was degassed at 400 ℃ for 300 min and sintered at 1150 ℃ for 500 min, and the xonotlite bioceramic porous scaffold was finally obtained.

[0067] Example 4

[0068] Surface structure modification of bioceramic porous scaffold:

[0069] (1) The first layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 7.5, mechanical stirring for 2 h, 76 g of β-tricalcium phosphate powder was added, and the stirring was continued for 6 h. The particle size of the β-tricalcium phosphate powder was D50 = 17 μm, and D90 = 25 μm.

[0070] (2) The second layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 7.5, mechanical stirring for 2 h, 41 g of xonotlite powder was added, and the stirring was continued for 6 h. The particle size of the xonotlite powder was D50 = 3 μm, and D90 = 6 μm.

[0071] (3) The 10 three-dimensional scaffolds obtained in Example 3 were first immersed in the first layer of impregnation solution, ultrasonic dispersion for 5 min, and the excess solution was shaken off. The dried scaffold was immersed in the second layer of impregnation solution, ultrasonic dispersion for 5 min, and the excess solution was shaken off. The dried scaffold was sintered at a temperature of 800 ℃ for 180 min, and a surface structure modified bioceramic porous scaffold was obtained.

[0072] Example 5

[0073] Surface structure modification of the bioceramic porous scaffold:

[0074] (1) The first layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 9.0, mechanical stirring for 10 min, 125 g of β-tricalcium phosphate powder was added, and the stirring was continued for 24 h. The particle size of the β-tricalcium phosphate powder was D50 = 23 μm, and D90 = 35 μm.

[0075] (2) The second layer of impregnation solution preparation: 2 g dopamine was added to 500 mL purified water, a small amount of Na2CO3 was added to adjust the solution pH to 9.0, mechanical stirring for 10 min, 75 g of xonotlite powder was added, and the stirring was continued for 24 h. The particle size of the xonotlite powder was D50 = 7 μm, and D90 = 10 μm.

[0076] (3) The 10 three-dimensional scaffolds obtained in Example 3 were first immersed in the first layer of impregnation solution, ultrasonically dispersed for 30 min, the excess solution was shaken off, and the dried scaffold was obtained by drying in an electric heating air drying oven at 90 ℃ for 1 h. The dried scaffold was immersed in the second layer of impregnation solution, ultrasonically dispersed for 30 min, the excess solution was shaken off, and the dried scaffold was obtained by drying in an electric heating air drying oven at 90 ℃ for 1 h. The dried scaffold was sintered at a sintering temperature of 1000 ℃ for 30 min, to obtain the surface structure modified bioceramic porous scaffold.

[0077] Comparative Example 1

[0078] This example is a comparative example. The wollastonite bioceramic porous scaffold obtained in Example 1 was immersed in the first layer of impregnation solution for impregnation treatment, to obtain a surface structure modified bioceramic porous scaffold.

[0079] The specific steps are as follows: the preparation of the first layer of impregnation solution and the particle size requirement of the powder are completely consistent with the operation process of step (1) in Example 2. The wollastonite bioceramic porous scaffold obtained in Example 1 was immersed in the first layer of impregnation solution, ultrasonically dispersed for 10 min, the excess solution was shaken off, and the dried scaffold was obtained by drying in an electric heating air drying oven at 60 ℃ for 3 h. The dried scaffold was sintered at a sintering temperature of 950 ℃ for 60 min, to obtain the surface structure modified bioceramic porous scaffold.

[0080] Comparative Example 2

[0081] This example is a comparative example. The wollastonite bioceramic porous scaffold obtained in Example 1 was immersed in two layers of impregnation solution for impregnation treatment, to obtain two layers of surface structure modified bioceramic porous scaffolds. The powder of the first layer of impregnation solution was bioactive glass 45S5, with a powder particle size of D50 = 4.5 μm and D90 = 8.6 μm. The powder of the second layer of impregnation solution was β-tricalcium phosphate, with a powder particle size of D50 = 19.8 μm and D90 = 31.1 μm. The remaining steps were completely consistent with Example 2.

[0082] Comparative Example 3

[0083] The sintering temperature in step (3) in Example 2 was replaced by 750 ℃, and the remaining preparation steps were consistent with those in Example 2.

[0084] Comparative Example 4

[0085] The sintering temperature in step (3) in Example 2 was replaced by 1100 ℃, and the remaining preparation steps were consistent with those in Example 2.

[0086] Test Example 1

[0087] The product performance of the application and the results are as follows:

[0088] (1) Total porosity and pore size distribution study:

[0089] The bioceramic scaffolds obtained from Example 1 and Example 2 were subjected to micro-CT scanning, and the pore size distribution and structure diagram of the porous scaffold before and after surface structure modification are shown in Figures 1-4 As shown in Figure 1 , before surface structure modification, the total porosity of the material was 60%, and the pore size distribution of the material was 91% in the range of 50-800 μm, and 45% in the range of 50-600 μm; as shown in Figure 3 , after surface structure modification, the total porosity of the material was 50%, and the pore size distribution was 99% in the range of 50-800 μm, and 85% in the range of 50-600 μm. The pore size distribution results show that after surface structure modification, the pore size of the scaffold material tends to be smaller, indicating that the powder in the immersion solution is successfully combined to the surface of the scaffold material, and after surface modification, the number of pores of each size presents a normal distribution, which is close to the pore size range of natural bone tissue. The pore size range of the scaffold is conducive to the growth of bone tissue (see Figure 2 Three-dimensional printed porous scaffold and Figure 4 Surface structure modified three-dimensional printed porous scaffold).

[0090] (2) Scanning electron microscopy study:

[0091] The bioceramic scaffolds obtained from Example 1 and Example 2 were observed under scanning electron microscope to observe the surface morphology of the scaffold, as shown in Figure 5 , compared with the surface structure modified three-dimensional printed porous scaffold (b1 and b2), the surface roughness of the surface structure modified three-dimensional printed porous scaffold is higher, so the surface structure modification improves the surface energy of the ceramic scaffold, which is conducive to the hydrophilicity, blood infiltration of the material, and the ion exchange of the interface, thereby promoting the growth of bone tissue.

[0092] (3) Hydrophilicity study:

[0093] The samples obtained from Example 1, 2, 4 and 5, Comparative Example 1, and Comparative Example 2 were subjected to hydrophilicity evaluation, and the specific operation steps are as follows:

[0094] The sample was weighed (recorded as m1) and placed in a beaker containing purified water, and was taken out and weighed (recorded as m2) after 30 s, 1 min, and 2 min, respectively. The water absorption rate of the sample was calculated according to the following formula:

[0095] Water absorption rate = (m2 - m1) / m1 × 100%

[0096] The water absorption test results are shown in Table 1. Compared with Example 1 and Example 3 (without surface structure modification), the water absorption of the surface structure modified scaffolds (Example 2, Example 4 and Example 5) is significantly improved. Comparative Example 1 is a scaffold modified with only one layer of large particle size, and Comparative Example 2 is a scaffold modified with a small particle size first and a large particle size later. The hydrophilicity of the scaffold is improved compared with Example 1. Among them, the scaffolds of Example 2, Example 4 and Example 5 are modified by two layers of powder coating, and the particle size of the two layers of powder is controlled within the specified range of the powder. The water absorption is the highest, and the water absorption basically reaches saturation in only 30 seconds. Therefore, the hydrophilicity of the scaffold obtained by the powder particle size is the best. The reason is that the ceramic scaffold without surface structure modification (Example 1 and Example 3) is sintered at high temperature, and the surface structure is relatively dense, the surface roughness of the material is low, the surface energy of the material is low, and the hydrophilicity is poor. After the scaffold surface is modified with powder and sintered at a lower temperature, the scaffold surface is modified with a relatively rough and loose structure, which improves the surface roughness of the material, thereby significantly improving the hydrophilicity. At the same time, the particle size of the modified powder is also very important. Modifying large particle size (D50 = 20 ± 3 μm, D90 = 30 ± 5 μm) first and small particle size (D50 = 5 ± 2 μm, D90 = 8 ± 2 μm) later makes the specific surface area of the material larger, so the hydrophilicity of Example 2 is better. In combination with Comparative Example 3 and Comparative Example 4, when the sintering temperature after immersion is not within 800-1000℃, the sintering temperature is lower than 800℃, the modified powder is not firmly combined with the scaffold surface, the surface structure modification is not obvious, and the hydrophilicity is poor. When the sintering temperature is higher than 1000℃, the modified powder forms a relatively dense structure on the scaffold surface, the surface roughness of the material is low, and the hydrophilicity is poor.

[0097] Table 1 Water absorption test results

[0098]

[0099] (4) Cytotoxicity and cell proliferation rate research:

[0100] The samples obtained from Example 1 and Example 2 were subjected to cytotoxicity and cell proliferation rate research experiments: human fibroblasts (MRC5) were used as a model, and the cell proliferation rate after 48h and 72h of culture was detected by MTT method. The test results are shown in Table 2, and the surface structure modified bioceramic porous scaffold has good cell compatibility. Figure 6

[0101] ​The above merely describes several embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical contents without departing from the scope of the technical solutions of the present application, and the equivalent embodiments are equivalent to the equivalent embodiments, which are within the scope of the technical solutions.

Claims

1. A method for preparing a surface-structure-modified bioceramic bone repair scaffold, characterized in that, The preparation method includes the following steps: Step S1: The mixture containing ceramic powder, photosensitive resin and dispersant is ball-milled, printed, debinded and sintered to obtain a porous three-dimensional scaffold. Step S2: The porous three-dimensional scaffold is impregnated in the impregnation solution to obtain a bioceramic bone repair scaffold with modified surface structure. The impregnation solution includes a first impregnation solution and a second impregnation solution; In the first impregnation solution, the powder particle size is D50=20±3μm and D90=30±5μm; In the second impregnation solution, the powder particle size is D50=5±2μm, D90=8±2μm; The impregnation solution includes water, powder, and dopamine; The powder is selected from at least one of the following: bioactive glass, β-tricalcium phosphate, α-tricalcium phosphate, leucosite, hydroxyapatite, calcium silicate, magnesium feldspar, and diopside. In step S2, the porous three-dimensional scaffold is immersed in the first impregnation solution 1, dried 1, then immersed in the second impregnation solution 2, dried 2, and sintered 2 to obtain a bioceramic bone repair scaffold with modified surface structure.

2. The preparation method according to claim 1, characterized in that, The concentration of dopamine in the impregnation solution is 2-8 g / L.

3. The preparation method according to claim 1, characterized in that, In the first impregnation solution, the mass percentage of powder in the solution is 15% to 25%.

4. The preparation method according to claim 1, characterized in that, In the second impregnation solution, the powder content is 8-15% by mass.

5. The preparation method according to claim 1, characterized in that, The method for preparing the impregnation solution includes: mixing water and dopamine, stirring for 10 min to 2 h, adding powder and mechanically stirring for 6 to 24 h to obtain the impregnation solution.

6. The preparation method according to claim 1, characterized in that, After the water and dopamine are mixed, the pH value is adjusted to 7.5~9.

0.

7. The preparation method according to claim 1, characterized in that, In step S2, the temperature of sintering 2 is 800~1000℃, and the sintering time is 30~180min.

8. The preparation method according to claim 1, characterized in that, The soaking times for immersion 1 and immersion 2 are independently selected from 5 to 30 minutes.

9. The preparation method according to claim 1, characterized in that, The temperatures for drying 1 and drying 2 are independently selected from 40 to 90°C, and the times for drying 1 and drying 2 are independently selected from 1 to 5 hours.

10. The preparation method according to claim 1, characterized in that, In step S1, the ceramic powder is selected from at least one of β-tricalcium phosphate, α-tricalcium phosphate, leucosite, hydroxyapatite, calcium silicate, magnesium feldspar, and diopside.

11. The preparation method according to claim 1, characterized in that, The photosensitive resin is selected from at least one of the commercially available photosensitive resins Ausbond A370 or Formlabs photosensitive resin.

12. The preparation method according to claim 1, characterized in that, The dispersant is selected from at least one of propylene glycol methyl ether, BYK-111, Triton X-100, KH-550, and KH-560.

13. The preparation method according to claim 1, characterized in that, The mass ratio of the ceramic powder, photosensitive resin, and dispersant is 1g:(0.3~0.5)g:(0.05~0.1)g.

14. The preparation method according to claim 1, characterized in that, The ball milling time is 28-56 hours.

15. The preparation method according to claim 1, characterized in that, The printing method is three-dimensional printing technology, and the forming accuracy of the three-dimensional printing technology is 30~100μm, wherein the pore size of the support is distributed in the range of 50~800μm, accounting for more than 85%.

16. The preparation method according to claim 1, characterized in that, In step S1, the temperature of the glue removal is 400~700℃, and the glue removal time is 180~300min.

17. The preparation method according to claim 1, characterized in that, In step S1, the temperature of sintering 1 is 1150~1450℃, and the sintering time is 120~500min.

18. A surface-structure-modified bioceramic bone repair scaffold prepared by the preparation method according to any one of claims 1 to 17.

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