CN112274701A - Photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing and preparation method thereof - Google Patents
Photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The invention belongs to the field of biological materials, and discloses photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing and a preparation method thereof. The beta-tricalcium phosphate powder is subjected to surface treatment by using a silane coupling agent, mixed with photosensitive resin to prepare composite ink, and then subjected to photocuring 3D printing and sintering to obtain the porous scaffold for bone tissue repair. The invention has the advantages of simple preparation method of the porous bracket, short forming time and the like, and is convenient for obtaining the bracket with high pore connectivity and controllable shape and size through structural design, so that the bracket can be more widely applied to the field of biomedicine.
Description
Technical Field
The invention belongs to the field of biological materials, and particularly relates to photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing and a preparation method thereof.
Background
Beta-tricalcium phosphate [ beta-Ca ]3(PO4)2]The components of the (beta-TCP) are similar to the inorganic components of human bone tissues, have higher solubility in body fluid than hydroxyapatite, can be slowly degraded, and are widely applied to the field of bone repair (particularly: Eliaz, N.,&meta, n.materials,2017,10(4), 334). After the beta-TCP is implanted into the defect part, calcium-phosphorus balance is formed on the upper interface and is deposited on the interface, so that the bone conduction function is good; the degradation of beta-TCP provides more abundant calcium and phosphorus ions, and promotes the generation of new bone tissue (specifically: Ma, H., Feng, C., Chang, J.,&wu, c. acta bionatrielia, 2018, 79, 37-59.). Research shows that the porous beta-tricalcium phosphate is more favorable to the proliferation, differentiation, metabolism and angiogenesis of cells.
The 3D printing technology is widely applied to biological material research in recent years, particularly has advantages of pore shape, structure and size design and manufacturing in the aspect of porous scaffold manufacturing, and can solve the problems of poor pore connectivity, difficulty in controlling the shape and size of pores and the like in the traditional method for preparing beta-tricalcium phosphate porous biological ceramics. For example, chinese patent publication CN107721408A provides a method for preparing beta-tricalcium phosphate porous bioceramic by SLA printing, which utilizes silane coupling agent to improve the performance of photocuring ceramic slurry, and obtains dense beta-tricalcium phosphate porous ceramic after photocuring molding and sintering. In addition, the chinese patent publication CN110092653A provides a preparation method of an extrusion type 3D printing degradable beta-tricalcium phosphate porous bioceramic scaffold, and the sintering temperature of the beta-tricalcium phosphate porous bioceramic scaffold is reduced by adding bioactive glass to solve the problems of slow degradation rate and low bioactivity of bone repair materials.
Disclosure of Invention
The invention aims to provide a photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing.
The invention further aims to provide a preparation method of the photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing, which is characterized in that the dispersibility of beta-tricalcium phosphate powder in resin is improved through modification of a silane coupling agent, and the degradable beta-tricalcium phosphate porous scaffold with a complex shape and high solid content is obtained through photocuring printing.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing comprises the following components:
photosensitive resin, beta-tricalcium phosphate ceramic powder, photoinitiator and silane coupling agent;
wherein the mass ratio of the beta-tricalcium phosphate powder to the photosensitive resin is 40-62: 38-60; the content of the beta-tricalcium phosphate ceramic powder accounts for 38.9-61.5 wt% of the total amount of the ink, the addition proportion of the photoinitiator accounts for 0.5-1.5 wt% of the photosensitive resin, and the addition proportion of the silane coupling agent accounts for 1-5 wt% of the beta-tricalcium phosphate ceramic powder.
The photosensitive resin is at least one of polyethylene glycol diacrylate, carboxyethyl acrylate (beta-CEA), triethylene glycol dimethacrylate (PEGDMA) and hexanediol diacrylate (HDDA). Preferably, the weight ratio of polyethylene glycol diacrylate, PEGDMA, HDDA and beta-CEA is 75-84: 0-16: 0-12: 13-16 by mixing.
The beta-tricalcium phosphate powder is particles with regular shapes close to spheres, and the particle size distribution range is 0.5-5 mu m.
The photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (BAPO) and the like.
The silane coupling agent is at least one of KH550, KH570 and the like.
A method for preparing the photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing comprises the following steps:
(1) adding beta-tricalcium phosphate powder into a silane coupling agent solution, and after the reaction is finished, purifying, drying and ball-milling to obtain surface-modified beta-tricalcium phosphate;
(2) and (2) uniformly mixing the surface modified beta-tricalcium phosphate obtained in the step (1), photosensitive resin and photoinitiator to prepare the 3D printing ink.
The mass volume ratio of the silane coupling agent solution in the step (1) is 8-12%, and preferably 10%; the pH value of the silane coupling agent solution is 4-5; the solvent of the silane coupling agent solution is ethanol and/or water and the like.
The reaction in the step (1) is carried out for 4-6 h at the temperature of 75-90 ℃; the ball milling time is 2-12 h.
A beta-tricalcium phosphate porous ceramic scaffold for DLP 3D printing is prepared by the following steps:
(1) pouring 3D printing ink into a resin tank of DLP printing equipment, designing a three-dimensional support model, and printing a porous ceramic support by a DLP printing technology;
(2) cleaning the printed porous ceramic support with an organic solvent, and then carrying out secondary curing; and (5) drying at normal temperature, and setting a sintering route for sintering to obtain the material.
And (2) the exposure time of the DLP printing in the step (1) is 1.1-1.9 s.
The sintering route of the porous ceramic support in the step (2) is as follows: raising the temperature from room temperature to 520-700 ℃ at a speed of 0.5-2.0 ℃/min, preserving the heat for 1-3 hours, then raising the temperature to 1000-1150 ℃ at a speed of 0.5-2 ℃/min, preserving the heat for 3-8 hours, and cooling along with the furnace.
The preparation method and the obtained sample have the following advantages and beneficial effects:
the degradable porous beta-tricalcium phosphate scaffold prepared by the 3D printing technology has good biocompatibility; can realize simple, convenient and quick printing of the porous scaffold with controllable structure, and is used for repairing tissues such as bones, teeth and the like.
The DLP 3D printing rapid forming technology is used, the material utilization rate is high, the forming speed is high, the mechanical strength is high, the mass production can be realized, and the economic benefit is better;
the porous biological ceramic scaffold can be customized according to the bone defect structure of a patient.
Drawings
FIG. 1 is a flow chart of the photocurable paste of examples 1, 2 and 3.
FIG. 2 is a schematic diagram of sintered ceramic scaffolds obtained in examples 1, 2, 3 and 4.
FIG. 3 is an SEM image of the surface topography of the ceramic scaffold obtained in example 2.
FIG. 4 shows the results of the biotoxicity test of the ceramic stent obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Adding beta-tricalcium phosphate powder into a 90% ethanol solution of KH550 for modification (the mass volume ratio is 10%), adding a silane coupling agent in a proportion of 1 wt% of the beta-tricalcium phosphate ceramic powder, reacting at 75 ℃ for 6 hours, drying, and performing ball milling treatment.
(2) Weighing 25g of polyethylene glycol diacrylate, 5g of PEGDMA and 0.15g of BAPO, mixing for 30 minutes by magnetic stirring, and standing for 1 day to obtain the photosensitive resin system.
(3) And adding 20.2g of modified beta-tricalcium phosphate ceramic powder into the photosensitive resin system in batches, and performing ultrasonic dispersion to obtain ceramic slurry.
(4) And adding the ceramic slurry into a trough of a photocuring printer, adjusting the exposure time to be 1.3s, opening the support model file subjected to slicing processing, and printing the support biscuit.
(5) And drying the biscuit, degreasing and sintering at high temperature to obtain the support. The sintering route is as follows: heating to 700 deg.C at 0.5 deg.C/min, holding for 1 hr, heating to 1000 deg.C at 2 deg.C/min, holding for 3 hr, and furnace cooling.
Example 2
(1) Adding beta-tricalcium phosphate powder into a 90% ethanol solution of KH550 for modification (the mass volume ratio is 10%), adding a silane coupling agent in a proportion of 2 wt% of the beta-tricalcium phosphate ceramic powder, reacting at 85 ℃ for 5 hours, drying, and performing ball milling treatment.
(2) 23g of polyethylene glycol diacrylate, 2g of HDDA, 5g of PEGDMA and 0.45g of BAPO were weighed, mixed for 30 minutes by magnetic stirring and left to stand for 1 day to obtain a photosensitive resin system.
(3) And adding 30.4g of modified tricalcium phosphate ceramic powder into the photosensitive resin system in batches, and performing ultrasonic dispersion to obtain ceramic slurry.
(4) And adding the ceramic slurry into a trough of a photocuring printer, adjusting the exposure time to be 1.4s, opening the support model file subjected to slicing processing, and printing the support biscuit.
(5) And drying the biscuit, degreasing and sintering at high temperature to obtain the support. The sintering route is as follows: heating to 600 deg.C at 0.8 deg.C/min, holding for 2.5 hr, heating to 1100 deg.C at 0.8 deg.C/min, holding for 3 hr, and furnace cooling.
Example 3
(1) Adding beta-tricalcium phosphate powder into a 90% ethanol solution of KH570 for modification (the mass volume ratio is 10%), adding a silane coupling agent in a proportion of 4 wt% of the beta-tricalcium phosphate ceramic powder, reacting at 75 ℃ for 6 hours, drying, and performing ball milling treatment.
(2) 22.4g of polyethylene glycol diacrylate, 2.6g of HDDA, 5g of CEA and 0.45g of BAPO were weighed, mixed for 30 minutes by magnetic stirring and left stand for 1 day to obtain a photosensitive resin system.
(3) Adding 45.4g of modified tricalcium phosphate ceramic powder into the photosensitive resin system in batches, and performing ultrasonic dispersion to obtain ceramic slurry.
(4) And adding the ceramic slurry into a trough of a photocuring printer, adjusting the exposure time to be 1.5s, opening the support model file subjected to slicing processing, and printing the support biscuit.
(5) And drying the biscuit, degreasing and sintering at high temperature to obtain the support. The sintering route is as follows: heating to 550 deg.C at 2 deg.C/min, holding for 2 hr, heating to 1100 deg.C at 1 deg.C/min, holding for 4 hr, and furnace cooling.
Example 4
(1) Adding beta-tricalcium phosphate powder into a 90% ethanol solution of KH570 for modification (the mass volume ratio is 10%), adding a silane coupling agent in a proportion of 5 wt% of the beta-tricalcium phosphate ceramic powder, reacting for 4 hours at 90 ℃, drying and carrying out ball milling treatment.
(2) 22.4g of polyethylene glycol diacrylate, 3.6g of HDDA, 4g of CEA and 0.3g of TPO are weighed, mixed for 30 minutes in a magnetic stirring manner and kept stand for 1 day to obtain a photosensitive resin system.
(3) 49.4g of modified tricalcium phosphate ceramic powder is added into the photosensitive resin system in batches for ultrasonic dispersion, and ceramic slurry is obtained.
(4) And adding the ceramic slurry into a trough of a photocuring printer, adjusting the exposure time to be 1.7s, opening the support model file subjected to slicing processing, and printing the support biscuit.
(5) And cleaning the biscuit, drying, degreasing and sintering at a high temperature to obtain the support. The sintering route is as follows: heating to 520 deg.C at 0.5 deg.C/min, holding for 1 hr, heating to 1150 deg.C at 2 deg.C/min, holding for 8 hr, and cooling with the furnace.
The ceramic slurry prepared in examples 1 to 3 was subjected to flow curve tests, and the results show that the viscosity of the slurry meets the viscosity requirement of printing, as shown in fig. 1.
For the β -tricalcium phosphate scaffolds prepared in examples 1-4, the material entities are shown in fig. 2.
The surface topography of the β -tricalcium phosphate scaffold prepared in example 2 was characterized and the results are shown in fig. 3. The results show that the sintered ceramic particles are bonded together, the particles are arranged more closely, no obvious cracks and holes exist on the surface, the surface is rough and fine micropores exist.
The β -tricalcium phosphate scaffold prepared in example 3 was characterized for cytotoxicity by leaching solution, and the results are shown in fig. 4. The results show that the survival rate of the cells of the scaffold from day 1 to day 3 is more than 90 percent, and the ceramic scaffold has no cytotoxicity.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, combinations, and alterations without departing from the spirit and principle of the present invention are all effective and encompassed in the scope of the present invention.
Claims (10)
1. The photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing is characterized by comprising the following components:
photosensitive resin, beta-tricalcium phosphate ceramic powder, photoinitiator and silane coupling agent;
wherein the mass ratio of the beta-tricalcium phosphate powder to the photosensitive resin is 40-62: 38-60; the content of the beta-tricalcium phosphate ceramic powder accounts for 38.9-61.5 wt% of the total amount of the ink, the addition proportion of the photoinitiator accounts for 0.5-1.5 wt% of the photosensitive resin, and the addition proportion of the silane coupling agent accounts for 1-5 wt% of the beta-tricalcium phosphate ceramic powder.
2. The photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing according to the comparison document 1 is characterized in that:
the photosensitive resin is at least one of polyethylene glycol diacrylate, carboxyethyl acrylate, triethylene glycol dimethacrylate and hexanediol diacrylate.
3. The photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing according to the comparison document 2 is characterized in that:
the photosensitive resin is polyethylene glycol diacrylate, triethylene glycol dimethacrylate, hexanediol diacrylate and carboxyethyl acrylate according to the mass ratio of 75-84: 0-16: 0-12: 13-16 by mixing.
4. The photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing according to the comparison document 1 is characterized in that: the particle size distribution range of the beta-tricalcium phosphate powder is 0.5-5 mu m.
5. The photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing according to the comparison document 1 is characterized in that: the photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide; the silane coupling agent is at least one of KH550 and KH 570.
6. A method for preparing the photosensitive resin/beta-tricalcium phosphate composite biological ink for DLP printing according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) adding beta-tricalcium phosphate powder into a silane coupling agent solution, and after the reaction is finished, purifying, drying and ball-milling to obtain surface-modified beta-tricalcium phosphate;
(2) and (2) uniformly mixing the surface modified beta-tricalcium phosphate obtained in the step (1), photosensitive resin and photoinitiator to prepare the 3D printing ink.
7. The method of claim 6, wherein:
the mass volume ratio of the silane coupling agent solution in the step (1) is 8-12%; the pH value of the silane coupling agent solution is 4-5; the solvent of the silane coupling agent solution is ethanol and/or water.
8. The method of claim 6, wherein:
the reaction in the step (1) is carried out for 4-6 h at the temperature of 75-90 ℃; the ball milling time is 2-12 h.
9. A DLP 3D printed beta-tricalcium phosphate porous ceramic scaffold is characterized by being prepared by the following steps:
(1) pouring the 3D printing ink obtained in any one of claims 1-5 into a resin tank of DLP printing equipment, designing a three-dimensional support model, and printing a porous ceramic support by a DLP printing technology;
(2) cleaning the printed porous ceramic support with an organic solvent, and then carrying out secondary curing; and (5) drying at normal temperature, and setting a sintering route for sintering to obtain the material.
10. The DLP 3D printed β -tricalcium phosphate porous ceramic scaffold of claim 9, characterized in that:
the exposure time of the DLP printing in the step (1) is 1.1-1.9 s;
the sintering route of the porous ceramic support in the step (2) is as follows: raising the temperature from room temperature to 520-700 ℃ at a speed of 0.5-2.0 ℃/min, preserving the heat for 1-3 hours, then raising the temperature to 1000-1150 ℃ at a speed of 0.5-2 ℃/min, preserving the heat for 3-8 hours, and cooling along with the furnace.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113800897A (en) * | 2021-08-17 | 2021-12-17 | 航天特种材料及工艺技术研究所 | Tricalcium phosphate biological ceramic for photocuring 3d printing, slurry thereof and preparation method thereof |
| CN114195526A (en) * | 2021-12-21 | 2022-03-18 | 山东大学 | Polyethylene glycol diacrylate/biological ceramic paste and forming and printing method |
| CN116474164A (en) * | 2023-05-26 | 2023-07-25 | 南京航空航天大学无锡研究院 | Bone repair stent with functional ion microcapsule and preparation method thereof |
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| CN111606719A (en) * | 2020-04-30 | 2020-09-01 | 西安增材制造国家研究院有限公司 | Photocuring 3D printing ceramic slurry and preparation method thereof |
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