CN107296985A - A kind of methods and applications based on Stereolithography 3 D-printing bioceramic scaffold - Google Patents

Abstract

The invention discloses a method for three-dimensionally printing bioceramic brackets based on photocuring molding. Firstly, bioceramic, bioglass sintering aid and resin premix are uniformly mixed to obtain photosensitive ceramic slurry; the photosensitive ceramic slurry is placed in photocuring molding On the equipment, according to the 3D model input into the molding machine, the body of the bioceramic stent is three-dimensionally printed; the body of the ceramic stent is dried, degreased, and sintered to obtain the bioceramic stent. The bioceramic scaffold has the characteristics of unlimited three-dimensional size, high strength, 100% three-dimensional pore connectivity, precise and controllable pore structure, etc., and has good application prospects in the field of bone defect repair materials.

Description

A method and application of three-dimensionally printed bioceramic scaffolds based on photocuring

technical field

The invention belongs to the technical field of biomanufacturing or biomedical materials, and more specifically relates to a method and application of a three-dimensionally printed bioceramic scaffold based on photocuring molding.

Background technique

Degradable bioceramics are the most common synthetic bone repair materials. Degradable bioceramic materials mainly include silicate ceramics, calcium phosphate ceramics and calcium carbonate ceramics. Degradable bioceramics are often made into porous scaffolds to provide space for the growth of bone tissue and cells, to achieve structural osteoconduction, and to promote the degradation and absorption of materials, thereby accelerating bone reconstruction and regeneration. At present, the molding and preparation methods of porous bioceramics mainly include pore-forming agent method, freezing casting method, gas foaming method, organic foam impregnation method, etc. Porous bioceramic scaffolds prepared by these methods are difficult to balance the relationship between pore structure and mechanical properties. Due to the inhomogeneous pore structure, there is a large stress concentration, and the mechanical properties of the scaffold deteriorate sharply with the increase of porosity, pore size, and three-dimensional connectivity. The pore structure of the porous bioceramic scaffold prepared by 3D printing (also called rapid prototyping or additive manufacturing) method is uniform and controllable, and the 3D pores are completely connected, which can obtain higher strength. The three-dimensional printing methods currently used to prepare porous bioceramic scaffolds are mainly three-dimensional drawing printing, inkjet printing, automatic grouting or fused deposition printing. The printing accuracy of these three-dimensional printing methods is low, the concentration of the ceramic slurry used is small, and the cohesive force of the water-based binder used is limited. , the porous stent body is easy to collapse and deform under the action of its own gravity. The height (Z-axis) of porous ceramic scaffolds prepared by these 3D printing methods is limited.

In summary, although the porous biodegradable bioceramic scaffold prepared by 3D printing has obvious advantages, it has the problems of low pore structure precision and limited three-dimensional size of the scaffold. The 3D printing technology based on photocuring has high precision and is mainly used to print photosensitive resin. By replacing the photosensitive resin with a ceramic-photosensitive resin mixed slurry, it is possible to three-dimensionally print ceramic blanks on a photocuring molding machine. Due to the high strength of the photosensitive resin used as a binder after curing, the 3D-printed ceramic green body by photocuring is not limited in size. Through the post-processing process (including drying, degreasing and sintering, etc.), the corresponding ceramic special-shaped parts can be finally obtained. At present, light curing molding technology has been successfully used in three-dimensional printing of alumina ceramics, zirconia ceramics, silicon oxide ceramics, lead zirconate titanate piezoelectric ceramics, etc. However, there are currently no relevant papers and patent reports on 3D printing of porous bioceramic scaffolds using photocuring technology. Forming technology 3D printed bioceramic scaffolds have a loose structure and low strength, which is difficult to meet the requirements of bone defect repair.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for three-dimensionally printing bioceramic scaffolds based on photocuring. By introducing low-melting-point bioglass as a sintering aid, this method can solve the problem of low strength of bioceramic scaffolds caused by excessive organic additives and poor sintering performance of bioceramics, and the use of photocuring 3D printing bioceramic scaffolds can obtain higher Precision hole structure, and the three-dimensional size (especially the Z axis) is not limited.

Another object of the present invention is to provide a bioceramic scaffold prepared by the above method, which has the advantages of unlimited three-dimensional size, precise and controllable pore structure, 100% three-dimensional pore connectivity and high strength, and has good Application prospects.

The above-mentioned purpose of the present invention is achieved through the following technical solutions:

A method for three-dimensionally printing a bioceramic support based on photocuring, comprising the following specific steps:

S1. Uniformly mix bioceramic, bioglass sintering aid and resin premix to obtain photosensitive ceramic slurry for photocuring molding;

S2. Place the photosensitive ceramic slurry on the photocuring molding equipment, input the three-dimensional model of the porous support into the photocuring molding machine, and three-dimensionally print the porous bioceramic support body through the photocuring molding method;

S3. After drying the porous bioceramic stent green body, degrease in vacuum, neutral atmosphere or inert atmosphere, then degrease in air and sinter to obtain the bioceramic stent.

Preferably, the bioceramic described in step S1 is one or more of calcium phosphate ceramics, silicate ceramics or calcium carbonate ceramics.

More preferably, the calcium phosphate ceramic is more than one of hydroxyapatite, calcium hydrogen phosphate, α-tricalcium phosphate or β-tricalcium phosphate, and the silicate ceramic is calcium silicate, More than one of dicalcium silicate, tricalcium silicate, feldspar, vitreousite or magnesium silicate, and the calcium carbonate ceramics are more than one of calcite, aragonite or vaterite.

Preferably, the bioglass sintering aid described in step S1 is phosphate glass or silicate glass, and the bioglass sintering aid contains magnesium, boron, silicon, zinc, iron, silver, copper or strontium More than one kind, the melting point of the bioglass sintering aid is 300-1150°C.

Preferably, the resin premix in step S1 includes a prepolymer, a diluent and a photoinitiator.

More preferably, the photosensitive resin prepolymer is polyurethane acrylate, epoxy acrylate, polyester acrylate or epoxy resin; the diluent is 2-phenoxyethyl acrylate (POEA), acrylic tetrahydrofuran Methyl ester (THFA), Propoxylated Neopentyl Glycol Acrylate, Diethylene Glycol Diacrylate Phthalate, Tricyclodecane Dimethanol Diacrylate, (2-Cyclohexyl-1,3-Dioxolane Cyclo-4) more than one of methyl acrylate (CHDOL10) or diethoxy bisphenol A diacrylate (EM260), the photoinitiator is benzoin (BE), benzoyl peroxide, isopropyl One or more of thioxanthone (ITX), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, or benzophenone.

Preferably, the mass ratio of the bioceramic and bioglass sintering aid in step S1 is 1: (0.1-1), and the total mass of the bioceramic and bioglass sintering aid is 20-20% of the photosensitive ceramic slurry. 80wt.%.

Wherein, the photo-curing molding machine described in step S2 adopts stereolithography technology or digital light projection technology, and the projection method of the photo-curing molding machine is top-down or bottom-up.

Preferably, the sintering temperature in step S3 is 700-1300° C., and the sintering time is 10-300 min; the inert atmosphere is argon or helium; the neutral atmosphere is nitrogen or carbon dioxide.

In step S3, degreasing in vacuum, neutral atmosphere or inert atmosphere, and then degreasing in air is used because the resin content is too much. If degreasing in air, the speed is very fast, which will cause severe cracking of the stent blank. In an inert atmosphere or a neutral atmosphere, it is almost removed by slow cracking into small molecules, or carbonization. However, the method of degreasing in vacuum, neutral atmosphere or inert atmosphere first, and then degreasing in air prevents the green body from cracking and makes the deformation smaller.

The bioceramic support prepared by the above method, the height of the bioceramic support (dimension in the Z-axis direction) is 0.1-1000 mm, the porosity is 20%-80%, the macropore diameter is 100-1000 μm, and the macroporosity is 25% ~75%, the compressive strength is 0.2~120MPa.

The application of the bioceramic support prepared by the above method in the field of bone defect repair materials.

Compared with the prior art, the present invention has the following beneficial effects:

1. Compared with the existing three-dimensionally printed bioceramic scaffolds by automatic grouting, three-dimensional drawing, inkjet printing and other methods, the present invention adopts photocuring and forming three-dimensionally printed bioceramic scaffolds to obtain a higher-precision pore structure, and the three-dimensional Dimensions (especially the Z axis) are not limited. By introducing low melting point bioglass as a sintering aid, the problem of low strength of bioceramic scaffolds caused by excessive organic additives and poor sintering performance of bioceramics can be solved.

2. The bioceramic scaffold prepared by the present invention has a porosity of 20% to 80%, a macropore diameter of 100 to 1000 μm, a macroporosity of 25% to 75%, and a compressive strength of 0.2 to 120 MPa, which can be used not only in non-load-bearing parts It can also be used for the repair of bone defects in some load-bearing parts.

3. The bioceramic scaffold prepared by the present invention can adjust the pore structure, mechanical properties and degradation rate of the scaffold by changing the three-dimensional model of the scaffold, the solid phase content of the photosensitive ceramic slurry, the amount of sintering aid added and the sintering process.

4. The bioceramic stent prepared by the present invention will release trace element ions such as iron, strontium, zinc, and copper after degradation, which is beneficial to osteogenesis and vascularization. At the same time, the ion concentration can be adjusted by changing the composition, structure, and sintering process. The regularity of release improves the osteogenesis and vascularization capabilities of the material.

detailed description

The content of the present invention will be further described below in conjunction with specific examples, but it should not be construed as a limitation of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

The preparation method of embodiment 1β-tricalcium phosphate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is urethane acrylate, the initiator is benzoyl peroxide, and the diluent is propoxylated neopentyl glycol acrylate. The powder of β-tricalcium phosphate and Sr-containing low-melting bioglass sintering aid (50P ₂ O ₅ -20Na ₂ O-30SrO) is evenly mixed with the photosensitive resin premix to obtain a photosensitive ceramic slurry with a solid phase content of 50%. The content of β-tricalcium phosphate in the ceramic slurry is 30%, and the content of the glass firing aid is 20%.

2. Input the three-dimensional model of the porous bracket into the photocuring molding machine; place the photosensitive ceramic slurry in step (1) on the DLP photocuring molding equipment, and the projection method is top-down, and the three-dimensional printing is performed by the photocuring molding method. Porous β-tricalcium phosphate ceramic stent body.

3. Freeze-dry the β-tricalcium phosphate ceramic stent body, put it into a high-temperature furnace, degrease it under a nitrogen atmosphere first, then slowly degrease it in the air, and finally raise the temperature in the air at a rate of 1°C/min, 1120 Sintering at ℃, keeping the temperature for 120 minutes, and cooling with the furnace temperature to obtain the β-tricalcium phosphate ceramic bioceramic support.

The obtained β-tricalcium phosphate ceramic bioceramic scaffold is completely connected with three-dimensional pores, and the pore diameter is about 400 μm. The porosity of the β-tricalcium phosphate scaffold measured by computer tomography (μ-CT) is 50%. The compressive strength of the bracket measured by the machine is 30MPa.

The preparation method of embodiment 2 calcium carbonate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is polyurethane acrylate, the initiator is benzoin (BE), and the diluent is propoxylated neopentyl glycol acrylate. The calcite-type calcium carbonate and Sr-containing biological glass sintering aid (50P ₂ O ₅ -20Na ₂ O-20CaO-10SrO) powder are evenly mixed with the photosensitive resin premix to obtain a photosensitive ceramic slurry with a solid phase content of 60%. The content of calcium carbonate in the ceramic slurry is 30%, and the content of glass sintering aid is 30%.

2. Input the three-dimensional model of the porous bracket into the photocuring molding machine; place the above-mentioned photosensitive ceramic slurry on the DLP photocuring molding equipment, and the projection method is bottom-up, and the designed porous structure is three-dimensionally printed by the photocuring molding method Calcium carbonate ceramic stent body.

3. Freeze-dry the calcium carbonate ceramic stent body, put it into a high-temperature furnace, degrease it under vacuum first, then degrease it in air, and finally heat it up at a rate of 2°C/min in a carbon dioxide atmosphere, and sinter it at 750°C. Keep it warm for 10 minutes, and cool down with the furnace temperature to obtain a calcium carbonate ceramic bioceramic support.

The obtained calcium carbonate bioceramic support is completely connected in three-dimensional pores, and the pore diameter is about 300 μm. The macroporosity of the calcium carbonate support is 40% as measured by computerized tomography (μ-CT), and the compression resistance of the support is measured by a universal material testing machine. The strength is 15MPa.

The preparation method of embodiment 3 calcium silicate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. Mix calcium silicate and B and Si-containing bioglass glass sintering aid (45SiO ₂ -29CaO-15Na ₂ O-4P ₂ O ₅ -7B ₂ O ₃ ) powder with the photosensitive resin premix to obtain a solid phase content of 55 % photosensitive ceramic paste. The content of calcium silicate in the ceramic slurry is 35%, and the content of glass sintering aid is 20%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the above-mentioned photosensitive ceramic slurry on the DLP photocuring molding equipment, and the projection method is bottom-up, and the designed porous carbonic acid is three-dimensionally printed by the photocuring molding method. Calcium ceramic stent body.

3. Air-dry the calcium silicate ceramic stent body naturally, put it into a high-temperature furnace, degrease it under argon, and then degrease it in the air; finally, heat it up at a rate of 1°C/min in the air, at 1120°C sintering at lower temperature, heat preservation for 90 minutes, and cooling with furnace temperature to obtain calcium silicate ceramic bioceramic support.

The obtained calcium carbonate bioceramic support is completely connected in three-dimensional pores, and the pore diameter is about 500 μm. The macroporosity of the calcium carbonate support is 55% as measured by computerized tomography (μ-CT), and the compression resistance of the support is measured by a universal material testing machine. The strength is 25MPa.

The preparation method of embodiment 4 hydroxyapatite ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. The hydroxyapatite and Mg-containing bioglass sintering aid (45P ₂ O ₅ -25Na ₂ O-10MgO) are evenly mixed with the photosensitive resin premix to obtain a photosensitive ceramic slurry with a solid phase content of 60%. The content of hydroxyapatite in the ceramic slurry is 45%, and the content of glass sintering aid is 15%.

2. Input the three-dimensional model of the porous bracket into the photocuring molding machine; place the photosensitive ceramic slurry in step 1 on the SLA photocuring molding equipment, and the projection method is top-down, and print out the designed 3D model through the photocuring molding method Porous hydroxyapatite ceramic scaffold body.

3. Vacuum dry the hydroxyapatite ceramic stent body, put it in a high-temperature furnace, degrease it under vacuum first, then degrease it in the air; Sintering, heat preservation for 90 minutes, and cooling with the furnace temperature to obtain a hydroxyapatite ceramic support.

The obtained hydroxyapatite bioceramic support is completely connected in three-dimensional pores, and the pore diameter is about 300 μm. The macroporosity of the calcium carbonate support is measured by computer tomography (μ-CT). The macroporosity of the calcium carbonate support is 50%. The compressive strength is 45MPa.

The preparation method of embodiment 5 feldspar ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is polyester acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. The feldspar and Sr-containing bioglass sintering aid (45P ₂ O ₅ -35Na ₂ O-30SrO) are evenly mixed with the photosensitive resin premix to obtain a photosensitive ceramic slurry with a solid phase content of 40%. The content of feldspar in the ceramic slurry is 25%, and the content of glass sintering aid is 15%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the photosensitive ceramic slurry in step (1) on the SLA photocuring molding equipment, and the projection method is from top to bottom, and three-dimensionally print out through the photocuring molding method The designed porous magnesian feldspar ceramic scaffold body.

3. Vacuum-dry the magnesia feldspar ceramic support body, put it into a high-temperature furnace, degrease it under nitrogen, and then degrease it in the air; finally raise the temperature in the air at a rate of 3°C/min, sinter it at 1300°C, and keep it warm After cooling for 150 minutes with the temperature of the road, a magnesian feldspar ceramic bioceramic support was obtained.

The obtained magnesia feldspar bioceramic support is completely connected in three-dimensional pores, and the pore diameter is about 400 μm. The macroporosity of the calcium carbonate support is 35% measured by computerized tomography (μ-CT), and the compression resistance of the support is measured by a universal material testing machine. The strength is 35MPa.

The preparation method of embodiment 6 hydroxyapatite/β-tricalcium phosphate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. Mix hydroxyapatite, β-tricalcium phosphate and Sr-containing bioglass sintering aid (50P ₂ O ₅ -35Na ₂ O-15SrO) with the photosensitive resin premix to obtain a photosensitive ceramic slurry with a solid phase content of 65%. material. The content of hydroxyapatite in the ceramic slurry is 18%, the content of β-tricalcium phosphate is 27%, and the content of glass sintering aid is 20%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the photosensitive ceramic slurry in step 1 on the DLP photocuring molding equipment, and the projection method is bottom-up, and print out the designed three-dimensional model through the photocuring molding method Porous hydroxyapatite/β-tricalcium phosphate ceramic scaffold body.

3. Freeze-dry the hydroxyapatite/β-tricalcium phosphate ceramic stent body, put it in a high-temperature furnace, degrease it under vacuum first, then degrease it in the air; finally degrease it in the air at a speed of 3°C/min Heating up, sintering at 1150° C., holding the temperature for 80 minutes, and cooling with the furnace temperature to obtain the hydroxyapatite/β-tricalcium phosphate bioceramic scaffold.

The obtained hydroxyapatite/β-tricalcium phosphate bioceramic scaffold is completely connected with three-dimensional pores, and the pore diameter is about 350 μm. The macroporosity of the calcium carbonate scaffold measured by computer tomography (μ-CT) is 40%. The compressive strength of the bracket measured by the testing machine is 50MPa.

The preparation method of embodiment 7 calcium silicate/β-tricalcium phosphate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. Mix calcium silicate, β-tricalcium phosphate, and Fe-containing bioglass sintering aid (45P ₂ O ₅ -30Na ₂ O-20CaO-10Fe ₂ O ₃ ) powder with the photosensitive resin premix liquid to obtain a solid phase content of 45% photosensitive ceramic paste. The content of calcium silicate in the ceramic slurry is 10% of calcium silicate, the content of β-tricalcium phosphate is 30%, and the content of glass sintering aid is 15%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the above-mentioned photosensitive ceramic slurry on the SLA photocuring molding equipment, and the projection method is top-down, and the designed porous silicon is three-dimensionally printed by the photocuring molding method Calcium acid/β-tricalcium phosphate ceramic stent body.

3. Air-dry the calcium silicate/β-tricalcium phosphate ceramic stent body naturally, put it in a high-temperature furnace, degrease under vacuum first, then degrease in air; finally degrease in air at a speed of 1.5°C/min Raise the temperature, sinter at 1120° C., keep the temperature for 300 minutes, and cool down with the furnace temperature to obtain the calcium silicate/β-tricalcium phosphate bioceramic scaffold.

The obtained hydroxyapatite/β-tricalcium phosphate bioceramic scaffold is completely connected with three-dimensional pores, and the pore diameter is about 450 μm. The macroporosity of the calcium carbonate scaffold measured by computer tomography (μ-CT) is 50%. The compressive strength of the bracket measured by the testing machine is 17MPa.

The preparation method of embodiment 8 calcium carbonate/hydroxyapatite ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. Aragonite-type calcium carbonate, hydroxyapatite and Zn, Sr-containing biological glass sintering aid (45P ₂ O ₅ -30Na ₂ O-20SrO-5ZnO) were uniformly mixed with the photosensitive resin premix to obtain a solid phase content of 50%. Photosensitive ceramic paste. The content of calcium carbonate in the ceramic slurry is 10%, the content of hydroxyapatite is 20%, and the content of glass sintering aid is 20%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the photosensitive ceramic slurry in step 1 on the DLP photocuring molding equipment, and the projection method is bottom-up, and print out the designed three-dimensional model through the photocuring molding method Porous calcium carbonate/hydroxyapatite ceramic scaffold body.

3. Air-dry the calcium carbonate/hydroxyapatite ceramic stent body naturally, put it into a high-temperature furnace, degrease under vacuum first, then degrease in air, and finally heat up at a rate of 4°C/min in a carbon dioxide atmosphere , sintered at 700° C., kept for 30 minutes, and cooled with the furnace temperature to obtain a calcium carbonate/hydroxyapatite bioceramic scaffold.

The obtained calcium carbonate/hydroxyapatite bioceramic support is completely connected with three-dimensional pores, and the pore diameter is about 350 μm. The macroporosity of the calcium carbonate/hydroxyapatite support measured by computer tomography (μ-CT) is 40%. The compressive strength of the bracket measured by the universal material testing machine is 28MPa.

The preparation method of embodiment 9 wollastonite/α-tricalcium phosphate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is polyester acrylate, the initiator is benzoin (BE), and the diluent is tricyclodecane dimethanol diacrylate. Mix silicate, α-tricalcium phosphate and B, Sr-containing phosphate glass sintering aid (47P ₂ O ₅ -35Na ₂ O-13SrO-5B ₂ O ₃ ) with the photosensitive resin premix to obtain a solid phase A photosensitive ceramic slurry with a content of 70%. The content of the doxonotlite in the ceramic slurry is 25%, the content of the hydroxyapatite is 25%, and the content of the glass sintering aid is 20%.

2. Input the three-dimensional model of the porous support into the photocuring molding machine; place the photosensitive ceramic slurry in step 1 on the DLP photocuring molding equipment, and the projection method is bottom-up, and print out the designed three-dimensional model through the photocuring molding method Porous wollastonite/α-tricalcium phosphate ceramic stent body.

3. Vacuum-dry the white wollastonite/α-tricalcium phosphate ceramic stent body, put it into a high-temperature furnace, degrease it under vacuum first, then degrease it in the air, and finally degrease it in the air at a speed of 3°C/min Heating up, sintering at 1100° C., holding the temperature for 120 minutes, and cooling with the furnace temperature to obtain the wrathite/α-tricalcium phosphate bioceramic support.

The obtained white wollastonite/α-tricalcium phosphate bioceramic scaffold is completely connected with three-dimensional pores, the pore diameter is about 330 μm, and the macroporosity of the calcium carbonate/hydroxyapatite scaffold measured by computer tomography (μ-CT) is 40 %, the compressive strength of the bracket measured by a universal material testing machine is 85MPa.

The method of embodiment 10 tricalcium silicate/α-tricalcium phosphate ceramic support

1. Configure the photosensitive resin premix, the prepolymer used is epoxy acrylate, the initiator is isopropylthioxanthone (ITX), and the diluent is tricyclodecane dimethanol diacrylate. Mix tricalcium silicate, α-tricalcium phosphate and Ag-containing bioglass sintering aid (47P ₂ O ₅ -25Na ₂ O-20CaO-8AgO) with the photosensitive resin premix to obtain a photosensitive resin with a solid phase content of 50%. ceramic slurry. The content of tricalcium silicate in the ceramic slurry is 22%, the content of α-tricalcium phosphate is 13%, and the content of glass sintering aid is 15%.

2. Input the three-dimensional model of the porous bracket into the photocuring molding machine; place the photosensitive ceramic slurry in step 1 on the SLA photocuring molding equipment, and the projection method is top-down, and print out the designed 3D model through the photocuring molding method Porous tricalcium silicate/α-tricalcium phosphate ceramic stent body.

3. Freeze-dry the tricalcium silicate/α-tricalcium phosphate ceramic stent body, put it in a high-temperature furnace, degrease it under nitrogen, then degrease it in the air, and finally degrease it in the air at a speed of 2°C/min. Heating up, sintering at 1120° C., holding the temperature for 150 minutes, cooling with the furnace temperature, and obtaining the tricalcium silicate/α-tricalcium phosphate bioceramic scaffold.

The obtained tricalcium silicate/α-tricalcium phosphate bioceramic scaffold is completely connected with three-dimensional pores, and the pore diameter is about 550 μm. The macroporosity of the calcium carbonate/hydroxyapatite scaffold measured by computer tomography (μ-CT) is 55%. %, the compressive strength of the bracket measured by a universal testing machine is 12MPa.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations and modifications made without departing from the spirit and principles of the present invention Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

1. a kind of method based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that including walking in detail below Suddenly：

S1. bioceramic, bio-vitric sintering aid are uniformly mixed with resin premixed liquid, obtained for the photosensitive of Stereolithography Ceramic slurry；

S2. light sensitive ceramics slurry is placed in Stereolithography equipment, the threedimensional model of porous support is input to and is light-cured into Type machine, porous bioceramic scaffold base substrate is gone out by Stereolithography method 3 D-printing；

S3. after porous bioceramic scaffold base substrate is dried, ungrease treatment under first vacuum, neutral atmosphere or inert atmosphere, Then degreasing is carried out in air, sintering obtains bioceramic scaffold.

2. the method according to claim 1 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that Bioceramic described in step S1 is one or more of calcium phosphate ceramic, silicate ceramics or calcium carbonate ceramics.

3. the method according to claim 2 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that Described calcium phosphate ceramic is one or more of hydroxyapatite, calcium monohydrogen phosphate, type alpha tricalcium phosphate or bata-tricalcium phosphate, described Silicate ceramics one or more of for calcium silicates, dicalcium silicate, tricalcium silicate, akermanite, bredigite or magnesium silicate, Described calcium carbonate ceramics are one or more of calcite, aragonite or vaterite.

4. the method according to claim 1 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that Bio-vitric sintering aid described in step S1 is phosphate glass or silicate glass, and described bio-vitric sintering aid contains One or more of magnesium, boron, silicon, zinc, iron, silver, copper or strontium element, the fusing point of described bio-vitric sintering aid for 300~ 1150℃。

5. the method according to claim 1 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that Resin premixed liquid described in step S1 includes photosensitive resin prepolymer, diluent and initiator.

6. the method according to claim 5 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that The photosensitive resin prepolymer is urethane acrylate, epoxy acrylate, polyester acrylate or epoxy resin；It is described dilute It is 2- benzene oxygen ethyl propylenes acid esters, acrylic acid tetrahydrofuran methyl esters, the third oxidation neopentyl glycol acrylate, phthalic acid to release agent Diethylene glycol diacrylate, Tricyclodecane Dimethanol diacrylate, (2- cyclohexyl -1,3- dioxolanyls -4) acrylic acid One or more of methyl esters, diethoxy bisphenol a diacrylate；The light trigger is styrax, benzoyl peroxide, different Double (2,4,6- trimethylbenzoyls) phosphine oxides of propyl group thioxanthone, phenyl or benzophenone more than one.

7. the method according to claim 1 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that Bioceramic described in step S1 and the mass ratio of bio-vitric sintering aid are 1：(0.1~1), described bioceramic and biology The gross mass of glass sintering aid is 20~80wt.% of light sensitive ceramics slurry.

8. the method according to claim 1 based on Stereolithography 3 D-printing bioceramic scaffold, it is characterised in that The temperature sintered described in step S3 is 700~1300 DEG C, and the time of sintering is 10~300min；The inert atmosphere is argon gas Or helium；The neutral atmosphere is nitrogen or carbon dioxide.

9. bioceramic scaffold prepared by the method as described in claim any one of 1-8.

10. application of the bioceramic scaffold in bone impairment renovation material field described in claim 9.