CN116253576A - Preparation method of personalized ceramic skull regeneration prosthesis - Google Patents
Preparation method of personalized ceramic skull regeneration prosthesis Download PDFInfo
- Publication number
- CN116253576A CN116253576A CN202310018552.4A CN202310018552A CN116253576A CN 116253576 A CN116253576 A CN 116253576A CN 202310018552 A CN202310018552 A CN 202310018552A CN 116253576 A CN116253576 A CN 116253576A
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- Prior art keywords
- skull
- prosthesis
- ceramic
- regeneration
- calcium phosphate
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Abstract
The invention discloses a preparation method of a personalized ceramic skull regeneration prosthesis, which comprises the following steps: s1, firstly reconstructing a three-dimensional model of a skull of a patient, then reconstructing a skull defect model by mirror images and Boolean operation by utilizing symmetry of the skull, designing a macroscopic hole structure unit, and reconstructing the defect model by using the unit; s2, outputting the model as a printing file, taking ceramic slurry as a raw material, and obtaining a prosthesis blank through 3D printing; s3, cleaning, drying and sintering the printed embryo body to obtain a calcium phosphate ceramic prosthesis; s4, adding the calcium phosphate ceramic restoration into a nitric acid solution or a trisodium phosphate aqueous solution for hydrothermal reaction treatment to obtain the personalized ceramic skull regeneration restoration with the in-situ whisker. The prosthesis has a macroscopic pore structure, a micropore structure generated by sintering and an in-situ whisker structure generated by hydro-thermal treatment, can meet the individual requirements of patients, has good osteoinductive property and mechanical strength, and has great significance for solving the difficult problem of skull defect regeneration and repair in clinic.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a preparation method of a personalized skull regeneration prosthesis.
Background
Congenital cranial deformities and acquired external wounds often result in cranial defects, which can heal themselves with smaller sizes, but are difficult to heal with larger sizes, particularly with cranial defects exceeding critical dimensions. The skull defect may cause serious problems such as skull malformation, skull defect syndrome and the like. Cranioplasty is commonly used in the clinic for the treatment of skull defects.
Cranioplasty refers to a procedure that uses autologous or allogeneic, natural or artificial materials as implants to implant the defect site to effect repair of the defect. The materials used in the cranioplasty mainly comprise autologous bone, metal materials, medical polymer materials, bioactive ceramics and the like. Autologous bone grafting is a common means for repairing skull defects, which does not generate immune rejection reaction and has a good bone repair effect, but autologous bone sources are limited, and particularly it is very difficult to obtain autologous bone with sufficient size when repairing large-sized bone defects. The synthetic metal material and medical polymer material (such as polyaryletherketone material) have better mechanical properties, but are biologically inert, cannot be biodegraded and cannot induce bone regeneration, require long-term implantation of patients, are easy to cause adverse effects on life of the patients, and have the risk of loosening after long-term implantation.
The components of the calcium phosphate ceramic are similar to the components of natural bones, the calcium phosphate ceramic has good biocompatibility and osteoinductive property, and the material can be slowly degraded along with the gradual growth of new bones, so that the regeneration and repair of bone defects can be realized. Along with the continuous improvement of the requirements of the bone repair materials in clinic, the innovative preparation method of the calcium phosphate ceramic is required, and the development of the calcium phosphate ceramic which can not only meet the continuous pursuit of the personalized accurate treatment in clinic, but also can accurately regulate and control the pore structure to accelerate the bone regeneration and has good mechanical properties is an urgent problem to be solved. The 3D printing technology has higher precision, can prepare the shape of a complex structure, and has the advantages of shorter development period, no need of using a die in the forming process, easy operation and the like. In recent years, a certain research has been conducted around the osteoinductive properties of 3D printed calcium phosphate ceramics, but 3D printed calcium phosphate ceramics have the disadvantage of insufficient osteoinductive properties.
Therefore, on the premise of guaranteeing the 3D printing personalized preparation of the calcium phosphate ceramic, the excellent osteoinductive property of the calcium phosphate ceramic is guaranteed, the mechanical property of the calcium phosphate ceramic is improved, the requirements of personalized skull defect regeneration and repair are met, and the problem to be solved at present is urgent.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a personalized ceramic skull restoration body, which is used for realizing personalized preparation of the skull restoration body, improving the osteoinductive performance of the calcium phosphate ceramic skull restoration body and solving the problem of poor physical performance of the traditional calcium phosphate ceramic skull restoration body.
The preparation method of the personalized ceramic skull regeneration prosthesis provided by the invention comprises the following steps:
s1, firstly reconstructing a three-dimensional model of a skull of a patient, then reconstructing a skull defect model by mirror images and Boolean operation by utilizing symmetry of the skull, designing a macroscopic hole structure unit, and reconstructing the defect model by using the unit;
the macroscopic pore structure is selected from one or a combination of a plurality of structures of a three-period minimum curved surface structure, a bone-like trabecular structure, a hexagonal closest packing structure and a diamond structure with variable aperture porosity;
s2, outputting the model as a printing file, taking ceramic slurry as a raw material, and obtaining a prosthesis blank through 3D printing;
s3, ultrasonically cleaning the printed prosthesis blank by using absolute ethyl alcohol, then placing the prosthesis blank in a 60 ℃ oven for drying for at least 4 hours, and then sintering to obtain the calcium phosphate ceramic prosthesis; wherein, the sintering process is as follows: placing the dried blank into a muffle furnace or a vacuum sintering furnace for sintering, degreasing and sintering at 300-600 ℃ for 1-4 h after reaching the maximum temperature; then ceramic sintering is carried out, the sintering temperature is 900-1200 ℃, and the sintering heat preservation is carried out for 1-4 hours.
S4, adding the sintered calcium phosphate ceramic prosthesis into a nitric acid solution or a trisodium phosphate aqueous solution for hydrothermal reaction treatment to obtain the personalized ceramic skull regeneration prosthesis with the in-situ whisker. If trisodium phosphate aqueous solution is used, the hydrothermal reaction temperature is 180 ℃, and the reaction time is 24 hours; if a nitric acid solution is used, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 12 hours. The hydrothermal reaction treatment is used to form in-situ whiskers to enhance the osteoinductive properties and mechanical strength of the prosthesis.
Preferably, in step S2, the ceramic slurry is prepared from raw materials such as calcium phosphate powder, photosensitive resin, surface modifier, dispersant, printing aid, and the like. The specific preparation method comprises the following steps: firstly, mixing the calcium phosphate powder with a surface modifier and absolute ethyl alcohol, performing ball milling for 8-12 hours, and then drying and sieving to obtain the modified calcium phosphate powder. And then mixing the modified calcium phosphate powder, the photosensitive resin, the dispersing agent and the printing auxiliary agent, and performing ball milling for 4-8 hours to obtain the ceramic slurry.
Wherein the calcium phosphate powder is selected from one or two of hydroxyapatite and tricalcium phosphate. Preferably, the calcium phosphate powder is a composite powder of hydroxyapatite and tricalcium phosphate.
The photosensitive resin is formed by mixing one or two of ethoxylated trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate with a photoinitiator Omnirad 819. Preferably, the photosensitive resin is mixed by a photoinitiator Omnirad819, ethoxylated trimethylol propane triacrylate, 1, 6-hexanediol diacrylate. Wherein, the mass ratio of the ethoxylated trimethylolpropane triacrylate to the 1, 6-hexanediol diacrylate is 1:1, and the addition amount of the photoinitiator is 3 percent of the total mass of the resin.
The printing auxiliary agent is at least one of carbon powder, graphite and graphene. The addition amount is 1 to 5 percent of the mass of the calcium phosphate powder. Preferably, the printing auxiliary agent is carbon powder, and the addition amount of the printing auxiliary agent is 1% of the mass of the calcium phosphate powder.
The surface modifier is one of stearic acid, oleic acid and fatty alcohol polyoxyethylene ether phosphate (MAEP). The addition amount of the surface modifier is 1 to 6 percent of the mass of the calcium phosphate powder. Preferably, the surface modifier is fatty alcohol polyoxyethylene ether phosphate (MAEP), and the addition amount is 6% of the mass of the calcium phosphate powder.
The dispersing agent is BYK-111 or BYK-333. The addition amount is 3-10% of the mass of the calcium phosphate powder. Preferably, the dispersant is BYK-111, and the addition amount is 5% of the mass of the calcium phosphate powder.
Preferably, in step S4, the hydrothermal treatment is carried out by using a trisodium phosphate aqueous solution with a concentration of 0.2 mol/L; the hydrothermal reaction temperature is 180 ℃ and the reaction time is 24 hours.
Preferably, in step S1, a three-dimensional model of the skull of the patient is reconstructed using the chemicals software and smoothed; then reconstructing a skull defect model by using symmetry of the skull by using one of Magics, rhino, C D and 3dsMax software; macroscopic pore building blocks were designed using one of the Solidworks, C4D, 3dsMax software and the defect model was reconstructed using the blocks.
In the step S1, the macroscopic pore structure is preferably a hexagonal closest packing structure, and two macroscopic pores, namely a spherical pore and a through hole, exist in the structure; the spherical holes are distributed according to hexagonal closest packing, and the cylindrical through holes are connected with adjacent spherical holes; the aperture of the spherical hole is 100-1000 mu m, the aperture of the through hole is 1/2-1/10 of that of the spherical hole, and the porosity of the prosthesis is 30% -70%.
The 3D printing mode can adopt a direct ink writing technology DIW, a fused deposition modeling FDM, a laser powder bed fusion technology and a light-cured surface modeling DLP technology. Preferably, the 3D printing mode is a light-cured surface molding DLP technology. The slice thickness is 50 μm, the light source wavelength is 405nm, and the light source power is 6.20mJ/cm 2 The monolayer exposure time was 2s.
The prepared personalized skull regeneration prosthesis has the characteristics of a multi-level structure. The multi-level structure comprises a micro-pore structure, a macro-pore structure and an in-situ whisker structure. The macroscopic pore structure is generated by a model design and a printing process; the micro-pore structure is produced by a sintering process; the in-situ whisker structure is generated by a hydrothermal reaction.
Compared with the prior art, the invention has the following advantages:
(1) The personalized skull regeneration prosthesis contour model is reconstructed from the skull CT of the patient, and has good fitting performance with the skull defect of the patient. The model size and profile can be varied to conform the prosthesis to the defect depending on the patient's defect site.
(2) The macroscopic pores can enhance the permeability of the prosthesis, promote the replacement of nutrient substances and metabolic wastes between the prosthesis and surrounding tissues, and accelerate the ingrowth of tissues. The micropores can enhance the surface roughness of the repair body, promote cell adhesion and accelerate the bone regeneration process. The in-situ whisker is generated on the surface of the prosthesis through hydrothermal reaction, and the in-situ whisker structure can enhance the specific surface area and the surface roughness of the prosthesis, promote cell adhesion, promote the osteoinductive performance of the prosthesis and accelerate the bone regeneration process. In addition, the whisker structure can inhibit crack growth of the prosthesis, so that the physical strength of the prosthesis is improved.
(3) The printing precision is improved by adding various resins and light absorbing materials into the printing slurry, so that the macroscopic pore structure is ensured to be consistent with the expected one; by adding the printing auxiliary agent into the printing slurry, the printed model has more abundant micropores after sintering, the surface roughness and the specific surface area of the model are improved, and the cell adhesion is promoted; the invention has great significance for the clinical treatment of skull defect and can generate larger economic value.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic diagram showing the external appearance of the prosthesis prepared in example 1.
Fig. 2 is a schematic diagram of the prosthetic unit structure of example 1.
Fig. 3 (a), 3 (b) and 3 (c) are SEM photographs of the prosthesis according to the present invention, which was not subjected to the hydrothermal treatment, SEM photographs of the prosthesis using the hydrothermal treatment with nitric acid, and SEM photographs of the prosthesis using the trisodium phosphate treatment, respectively.
Fig. 4 is a schematic diagram of the prosthetic unit structure of example 2.
Fig. 5 shows compressive stress/displacement of the spherical pore structure and diamond structure prepared according to the present invention before and after a hydrothermal treatment.
FIG. 6 is a H & E staining chart of tissue sections taken from the prosthesis of example 1 after 6 months of implantation.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Modeling software used in the embodiment of the invention is as follows: solidWorks, magics, mimics. Other modeling software in the prior art, such as Rhino, 3dsMax, C4D, etc., are also suitable for use with the present invention.
Example 1
In this example, a calcium phosphate prosthesis for use in repairing beagle skull defects was designed and prepared. The method comprises the following steps:
(1) Design of an osteoinductive calcium phosphate ceramic skull prosthesis model: first, a beagle head skull model is reconstructed from beagle head CT data in chemicals. The skull defect is then created in Magics and a model of the skull defect location is reconstructed by mirroring and boolean operations using the symmetry of the skull. And constructing a model pore structure unit in Solidworks, wherein the unit body is of a hexagonal closest packing imitation lattice structure, the pore diameter of spherical pores is 560 mu m, the pore diameter of through pores is 200 mu m, and the porosity is 65%. The skull defect contours are then reconstructed in Magics with macroscopic hole unit structures by permutation and boolean operation to obtain a model of the skull defect prosthesis with macroscopic holes and to derive the print file in terms of a print layer thickness of 50 μm.
(2) Powder modification: 100g of calcium phosphate powder (hydroxyapatite: beta-tricalcium phosphate=0.33:0.67) is weighed, 6g of surface modifier MAEP (MAEP) and 80ml of ethanol are uniformly mixed, ball-milled and mixed, the rotating speed of the ball mill is 300r/min, ball-milled is carried out for 10 hours, the mixed powder is dried for 12 hours in the environment of 60 ℃ after ball-milling is finished, and then the dried powder is screened by a 100-mesh screen.
(3) Preparing ceramic slurry: 42g of the modified calcium phosphate powder obtained in the step (2), 1.74g of a photoinitiator Omnirad819, 58g of ethoxylated trimethylolpropane triacrylate, 2.1g of a dispersant BYK-111 and 0.42g of carbon powder are weighed, ball-milled and mixed for 8 hours, and the rotational speed of the ball mill is 300r/min, so that ceramic slurry is obtained.
(4) And (3) printing a model: the printed file is led into a photo-curing printer, the wavelength of a light source is set to be 405nm, and the power of the light source is 6.2mJ/cm 2 The exposure time is 2s, then printing is started by adopting the prepared ceramic slurry, and the model blank is taken off from the forming table after printing is finished.
(5) Treating and sintering a blank: the obtained printing embryo body is placed in a beaker filled with absolute ethyl alcohol, and then is placed in an ultrasonic cleaner for ultrasonic treatment for 15min. Taking out the embryo body after ultrasonic treatment for 3 times, and putting the embryo body into a 60 ℃ oven for drying for 8 hours. Putting the dried green body into a muffle furnace, heating the furnace to 300 ℃ from room temperature at a heating rate of 2.5 ℃/min under the air atmosphere, and preserving heat for 2 hours; then heating to 550 ℃ at a heating rate of 1 ℃/min, and preserving heat for 2 hours; then heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and finally cooling along with a furnace to obtain the calcium phosphate ceramic prosthesis.
(6) Hydrothermal reaction: the resulting calcium phosphate ceramic prosthesis was rinsed with ultrapure water, then added to a hydrothermal vessel, and 80ml of a trisodium phosphate aqueous solution having a concentration of 0.2mol/L was added to the hydrothermal vessel. Then adding the hydrothermal kettle into a baking oven, adjusting the temperature of the baking oven to 180 ℃ and keeping the temperature for 24 hours, and then starting to naturally cool. And taking out the prosthesis after the temperature of the hydrothermal kettle is reduced to room temperature, and flushing the prosthesis by using ultrapure water to obtain the required osteoinductive calcium phosphate ceramic prosthesis. The appearance of the prepared prosthesis is shown in fig. 1. The prosthesis unit structure is shown in fig. 2.
Fig. 3 is a SEM photograph comparison of the prosthesis not subjected to the hydrothermal treatment with nitric acid and the treatment with trisodium phosphate. In the figure, (a) is the prosthesis obtained in step (5) of example 1, which was not subjected to the hydrothermal treatment, (b) is the prosthesis obtained in step (6) which was subjected to the hydrothermal treatment with nitric acid, and (c) is the prosthesis obtained in step (6) which was subjected to the treatment with trisodium phosphate. From the figure, it can be seen that the ceramic without hydrothermal treatment is of a classical ceramic structure, obvious crystal boundaries are distributed among ceramic grains, and the surface of the granular ceramic is relatively smooth. And a large number of whisker structures grow in situ on the ceramic subjected to the hydrothermal treatment, and hexagonal rod-shaped whiskers or hollow tubular whisker structures grow on the surface, so that the specific surface area and the ceramic surface roughness are increased. Meanwhile, the whiskers are mutually staggered, so that the ceramic crack propagation can be effectively prevented, and the mechanical property can be improved.
Example 2
In this example, compared with example 1, the unit body used had a diamond structure. The cell rod diameter was 320 μm, the pore diameter was 600 μm, and the porosity was 60%. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared. The unit structure of the prosthesis is shown in fig. 4.
Fig. 5 is a compressive strength compression stress/displacement diagram of the simulated hexagonal close-packed structure prepared in example 1 and the diamond structure prepared in example 2 before and after the hydrothermal treatment. As can be seen from the figure, the compressive strength of the diamond-structured ceramic restoration without hydrothermal treatment, with nitric acid hydrothermal treatment and with trisodium phosphate hydrothermal treatment is 0.47MPa, 0.53MPa and 0.61MPa, respectively; the compressive strength of the ceramic prosthesis with the imitated hexagonal closest packing structure which is not subjected to the hydrothermal treatment, the nitric acid hydrothermal treatment and the trisodium phosphate hydrothermal treatment is 2.59MPa, 4.28MPa and 3.44MPa respectively. For the two structures of the diamond structure and the hexagonal closest packing imitation structure, the mechanical property of the ceramic restoration body subjected to the hydrothermal treatment is greatly improved compared with that of the ceramic restoration body not subjected to the hydrothermal treatment. Whereas the improvement of the mechanical properties of the trisodium phosphate hydrothermally treated prosthesis and the nitric acid hydrothermally treated ceramic prosthesis is related to the structure itself. The relevant data are shown in table 1.
TABLE 1 hydrothermal front-to-back compressive Strength of diamond Structure and hexagonal-like closest packing Structure restoration
Example 3
In this example, compared with example 1, the unit cell used had a square hole structure. The unit body rod width is 300 μm, the square hole width aperture is 500 μm, and the porosity is 68%. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Example 4
In this example, compared with example 1, a mixture of 1.74g of the photoinitiator Omnirad819, 58g of the ethoxylated trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate was used as the photosensitive resin. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Example 5
In this example, oleic acid was used as the surface modifier in an amount of 6g as compared with example 1. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Example 6
In this example, stearic acid was used as the surface modifier in an amount of 6g compared with example 1. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Example 7
In this example, compared with example 1, the degreasing sintering temperature was 600 ℃, the degreasing sintering temperature rise rate was 0.3 ℃/min, and the holding time was 4 hours. The sintering temperature of the ceramic is 1150 ℃ and the heat preservation time is 4 hours. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Example 8
In this example, compared with example 1, the solution used for the hydrothermal treatment was a nitric acid solution, the reaction temperature was 200℃and the reaction time was 12 hours. The rest preparation conditions are the same, and the personalized skull regeneration prosthesis is prepared.
Test example: animal in vivo implantation evaluation material osteoinductive
1. Test materials: the porous calcium phosphate ceramic prepared in example 1.
2. The experimental object: beagle 2 dogs, offered by the university of Sichuan China laboratory animal center.
3. The test method comprises the following steps: samples were implanted on both sides of the back muscle of 2 beagle dogs, 4 samples were implanted on the back of each beagle dog, and 8 samples were taken in parallel, and the porous calcium phosphate ceramic prepared in example 1 was used as the sample. Selecting back muscles of beagle as material implantation positions, placing support materials on two sides of the blunt separation muscles after the blunt separation muscles are in a bag shape, and stitching the muscles, fascia and skin layer by layer. The materials are obtained after operation, the samples are prepared into paraffin sections after 5um through the steps of fixing, dehydrating, transparentizing, paraffin embedding and the like, and H & E staining is adopted to examine the osteoinductive property of the materials.
4. The test results are shown in FIG. 6. As can be seen from the H & E section, after the material is implanted into the muscle for 6 weeks, a plurality of new bone tissues are generated in the hole, which proves that the material has better osteoinductive property and better application prospect in the regeneration and repair of clinical bone defects.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (7)
1. The preparation method of the personalized ceramic skull regeneration prosthesis is characterized by comprising the following steps:
s1, firstly reconstructing a three-dimensional model of a skull of a patient, then reconstructing a skull defect model by mirror images and Boolean operation by utilizing symmetry of the skull, designing a macroscopic hole structure unit, and reconstructing the skull defect model by using the unit;
the macroscopic pore structure is selected from one or a combination of a plurality of structures of a three-period minimum curved surface structure, a bone-like trabecular structure, a hexagonal closest packing structure and a diamond structure with variable aperture porosity;
s2, outputting the model as a printing file, taking ceramic slurry as a raw material, and obtaining a prosthesis blank through 3D printing;
s3, cleaning, drying and sintering the printed embryo body to obtain a calcium phosphate ceramic prosthesis; wherein, degreasing and sintering are firstly carried out in the sintering process, the temperature is 300-600 ℃, and the heat is preserved for 1-4 hours after the maximum temperature is reached; then ceramic sintering is carried out, the sintering temperature is 900-1200 ℃, and the sintering heat preservation is carried out for 1-4 hours;
s4, adding the sintered calcium phosphate ceramic prosthesis into a nitric acid solution or a trisodium phosphate aqueous solution for hydrothermal reaction treatment to obtain the personalized ceramic skull regeneration prosthesis with the in-situ whisker.
2. The method for preparing the personalized ceramic skull regeneration prosthesis according to claim 1, wherein in the step S2, the ceramic slurry is prepared from five raw materials of calcium phosphate powder, photosensitive resin, surface modifier, dispersing agent and printing auxiliary agent; wherein, the calcium phosphate powder is selected from one or two of hydroxyapatite and tricalcium phosphate;
the photosensitive resin is formed by mixing one or two of ethoxylated trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate with a photoinitiator Omnirad 819;
the surface modifier is one of stearic acid, oleic acid and fatty alcohol polyoxyethylene ether phosphate;
the dispersant is selected from BYK-111 or BYK-333;
the printing auxiliary agent is at least one of carbon powder, graphite and graphene.
3. A method of preparing a personalized ceramic skull regeneration prosthesis according to claim 2, wherein the method of preparing the ceramic slurry comprises: firstly, modifying calcium phosphate powder by adopting a surface modifier to obtain modified calcium phosphate powder; and then mixing the modified calcium phosphate powder, photosensitive resin, dispersing agent and printing auxiliary agent, and performing ball milling to obtain ceramic slurry.
4. A method for preparing a personalized ceramic skull regeneration prosthesis according to claim 3, wherein in step S3, the printed prosthesis embryo is ultrasonically cleaned with absolute ethanol, then dried in an oven at 60 ℃ for at least 4 hours, and then sintered.
5. A method for preparing a personalized ceramic skull regeneration prosthesis according to claim 4, wherein in step S4, if trisodium phosphate aqueous solution is used, the hydrothermal reaction temperature is 180 ℃, and the reaction time is 24 hours; if a nitric acid solution is used, the hydrothermal reaction temperature is 200 ℃ and the reaction time is 12 hours.
6. The method for preparing a personalized ceramic skull regeneration prosthesis according to claim 1, wherein in the step S1, the macroscopic pore structure is a hexagonal closest packing structure, and two macroscopic pores, namely a spherical pore and a through hole, exist in the structure; the spherical holes are distributed according to hexagonal closest packing, and the cylindrical through holes are connected with adjacent spherical holes; the aperture of the spherical hole is 100-1000 mu m, the aperture of the through hole is 1/2-1/10 of that of the spherical hole, and the porosity of the prosthesis is 30% -70%.
7. The method for preparing the personalized ceramic skull regeneration prosthesis according to claim 1, wherein in the step S1, a three-dimensional model of the skull of the patient is reconstructed by using Mimics software and is subjected to smoothing treatment; then reconstructing a skull defect model by using symmetry of the skull by using one of Magics, rhino, C D and 3dsMax software; macroscopic pore building blocks were designed using one of the Solidworks, C4D, 3dsMax software and used to reconstruct a skull defect model.
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