CN112552035A - Inducible bioactive 3D printing ceramic and preparation method thereof - Google Patents

Inducible bioactive 3D printing ceramic and preparation method thereof Download PDF

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CN112552035A
CN112552035A CN202011460720.8A CN202011460720A CN112552035A CN 112552035 A CN112552035 A CN 112552035A CN 202011460720 A CN202011460720 A CN 202011460720A CN 112552035 A CN112552035 A CN 112552035A
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ceramic
printing
slurry
calcium sulfate
bioactive
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张旗
张铁
蔡林
蔡志祥
闫飞飞
胡丽
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Hubei Lianjie Biomaterials Co ltd
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Hubei Lianjie Biomaterials Co ltd
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Abstract

The invention belongs to the technical field of biomedical materials, and discloses an inducible bioactive 3D printing ceramic which is prepared by dipping a porous 3D printing calcium silicate ceramic bracket into calcium sulfate-based repair slurry, and then carrying out solidification and freeze drying; the porous 3D printing calcium silicate ceramic support is prepared by preparing ceramic slurry from calcium silicate powder and photosensitive resin premixed liquid, and then carrying out photocuring 3D printing and degreasing sintering according to a design model. The biological ceramic obtained by the invention has good biological activity, degradation performance and osteogenesis performance, can realize personalized customization, and meets various requirements of patients.

Description

Inducible bioactive 3D printing ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to an inducible bioactive 3D printing ceramic and a preparation method thereof.
Background
3D printing is used as an emerging manufacturing technology, is rapidly developed in recent years, is applied to various industries, and has an irreplaceable position in the medical industry due to the unique forming advantages. Wherein Selective Laser Sintering (SLS) technology has been applied to the manufacturing and forming of metal medical devices, and the treatment effect shows more satisfactory results than the traditional process. Common 3D printing techniques are also Fused Deposition Modeling (FDM) and Stereolithography (SLA), where SLA has a higher precision and enables more complex model printing.
The main components of the traditional biological ceramic material are calcium phosphate and hydroxyapatite, the ceramic has better biocompatibility and mechanical property, but the degradation performance is poor, and the ceramic is difficult to degrade after being implanted into a body; and has no bioactivity, and can inhibit new bone formation. In the existing research of 3D printing ceramic, researchers generally increase the degradation speed and the osteogenic property of the material by increasing the porosity of the material, but the result is not ideal. Therefore, the development of the biological ceramic with good degradation performance and biological activity has important research and application significance.
Disclosure of Invention
The invention mainly aims to provide an inducible bioactive 3D printing ceramic which has good bioactivity, degradation performance and osteogenesis performance, can realize personalized customization and meet various requirements of patients, and the related preparation method is simple and is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
an inducible bioactive 3D printing ceramic is prepared by dipping a porous 3D printing calcium silicate ceramic bracket in calcium sulfate-based repair slurry, solidifying, and freeze-drying; the 3D printing calcium silicate ceramic support is formed by preparing ceramic slurry from calcium silicate powder and photosensitive resin premixed liquid, and then carrying out photocuring 3D printing and degreasing sintering according to model design.
Preferably, the decalcified bone matrix is further introduced into the porous 3D printed calcium silicate ceramic scaffold filled with the calcium sulfate-based repair slurry prior to solidification, freeze-drying.
In the scheme, the porous 3D printing calcium silicate ceramic support comprises a large-pore structure and a small-pore structure, wherein the size of the small pore is 400-1000 mu m, and the size of the large pore is more than 2 mm.
In the scheme, the porosity of the porous 3D printing calcium silicate ceramic support is 20-75%.
In the scheme, the calcium sulfate-based repair slurry is water-based slurry of calcium sulfate-based repair components, wherein the solid-to-liquid ratio of the calcium sulfate-based repair components to water is 1g: 0.23-0.50 mL.
In the scheme, the calcium sulfate-based repair component is calcium sulfate hemihydrate or a compound of the calcium sulfate-based repair component and a functional component; wherein the content of the calcium sulfate hemihydrate is 95-99.9 wt%.
In the above scheme, the functional component is an antibiotic, deferoxamine, a magnesium salt or a strontium salt.
In the scheme, the particle size of the decalcified bone matrix is 100-900 microns; the particle size of the calcium silicate is less than 10 mu m.
In the above scheme, the photosensitive resin premix comprises the following components in parts by weight: 95-98 parts of acrylate, 1-3 parts of photoinitiator and 1-4 parts of dispersant.
The preparation method of the inducible bioactive 3D printing ceramic comprises the following steps:
1) adding calcium silicate powder into the photosensitive resin premix, and uniformly mixing under normal pressure to obtain ceramic slurry;
2) adding the ceramic slurry obtained in the step 1) into a charging basket of a three-dimensional photocuring forming printer;
3) creating a porous model by using three-dimensional modeling software, and introducing the porous model into a three-dimensional photocuring molding printer;
4) adjusting photocuring printing parameters to enable the ceramic slurry to be stacked and formed layer by layer, and cleaning the uncured slurry to obtain a ceramic support biscuit;
5) placing the obtained ceramic support biscuit in a muffle furnace for degreasing and sintering to obtain a porous 3D printed calcium silicate ceramic support;
6) uniformly mixing the calcium sulfate-based repair component with water in proportion to prepare calcium sulfate-based repair slurry;
8) putting the obtained 3D printed calcium silicate ceramic bracket into the obtained calcium sulfate-based repair slurry, and stirring or ultrasonically treating to ensure that the calcium sulfate-based repair slurry is fully filled into the pore channel structure of the bracket;
9) introducing the decalcified bone matrix into the macroporous pores filled with the calcium sulfate-based repair slurry, curing at normal temperature, and freeze-drying to obtain the inducible bioactive 3D printing bioceramic.
In the scheme, the mass ratio of the calcium silicate powder to the photosensitive resin premix is 60-80: 20-40.
In the above scheme, the photocuring printing parameters include: the exposure intensity is 700-1000 mw/cm2The exposure time is 1-60 s, and the paving thickness is 10-100 μm.
In the above scheme, the degreasing sintering system is set as follows: firstly, heating to 250-350 ℃ at the speed of 0.5-10 ℃/min, and preserving heat for 2-3 h; then heating to 550-650 ℃ at the speed of 0.5-10 ℃/min, and preserving heat for 2-3 h; heating to the sintering temperature at the speed of 2-5 ℃/min, preserving the heat for 2-3 h, and finally naturally cooling to the room temperature; wherein the sintering temperature is 1100-1200 ℃.
Compared with the conventional calcium phosphate ceramic, the biological ceramic has good degradation performance and osteogenic performance, and ensures that a bone grafting area is finally and completely replaced by new bones; the single calcium silicate has poor biological activity, only a small amount of hydroxyapatite can be formed on the surface, the material is alkaline, the leaching is carried out under the proportion of 0.2g/mL, the pH value reaches more than 10, and the biocompatibility is poor; the invention firstly proposes a means of adopting a porous ceramic bracket to realize effective combination of calcium sulfate, decalcified bone matrix and calcium silicate-based biological ceramic, and overcomes the technical bottleneck that calcium sulfate-based repair components and the decalcified bone matrix are difficult to introduce into the biological ceramic (calcium sulfate cannot be subjected to photocuring 3D printing and sintering molding, and DBM is inactivated at a temperature of more than 50 ℃); in addition, the calcium silicate ceramic and the calcium sulfate are used in a matched manner, so that on one hand, the pH value of the calcium silicate ceramic can be reduced, the biocompatibility is improved, meanwhile, the calcium sulfate can make up for the defect of slow release of calcium ions of the calcium silicate, more calcium ions can be gathered on the interface of a material system and water after the calcium sulfate is introduced, a apatite layer can be formed on the surface of the material, the adhesion of cells is facilitated, the biological activity and the biocompatibility of the material system are increased, and the bone growth is promoted; calcium sulfate is compounded with functional materials such as antibiotics, deferoxamine, magnesium salts, strontium salts and the like, so that the functional materials can be slowly released in the degradation process, and the functions of the materials (such as the function of promoting vascularization of the deferoxamine) can be more effectively exerted; the introduced decalcified bone matrix can enable the material to have bone induction capability, so that internal bone formation and bone conduction are simultaneously carried out, bone formation is accelerated, and bone defects are quickly healed; the invention can realize the synchronous load of calcium sulfate and decalcified bone matrix in calcium silicate biological ceramics, and generate synergistic action, thereby obtaining a perfect bone implant material.
According to the invention, a three-dimensional photocuring molding 3D printing technology is adopted, so that the bionic microstructure and diversified structure of the product can be realized, and the clinical customization can be realized; compared with other forming modes, the product has high precision, better mechanical strength and high utilization rate of raw materials, and is easy to realize large-scale production.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes that a porous support mode is adopted to realize the effective load of calcium sulfate and decalcified bone matrix in the calcium silicate biological ceramic, and the obtained 3D printing ceramic has excellent biological activity and degradation performance and can obviously improve the osteogenic performance of the material;
2) calcium sulfate in the early stage of the obtained 3D printing ceramic is degraded, a phosphorite layer is formed on the surface of the material, cell aggregation is facilitated, and meanwhile, along with the degradation of the calcium sulfate, the ceramic forms a porous support, so that the growth of cells is facilitated; meanwhile, the calcium silicate has better degradation performance and can be completely replaced by bone tissues finally;
3) according to the invention, by combining the structural design of the ceramic support and the optimized degreasing and sintering process, the mechanical property and the use stability of the obtained 3D printing ceramic can be effectively ensured;
4) the bionic microstructure can be realized, and the osteogenesis is accelerated; personalized customization can be realized, and the bone grafting requirement of special parts is met;
5) has bone induction ability, and can accelerate bone healing.
Drawings
FIG. 1 is a topographical view of a porous 3D-printed calcium silicate ceramic scaffold obtained by using the 3D printing technique described in the present invention;
FIG. 2 is a topography of a 3D printed bioceramic obtained after filling a calcium sulfate-based repair slurry into a porous 3D printed calcium silicate ceramic scaffold and curing (and removing calcium sulfate-based components in macropores);
fig. 3 is an XRD pattern of the inducible bioactive 3D printed ceramics obtained in comparative example 2(a) and example 2 (b).
Fig. 4 is an SEM image of the 3D printed ceramics obtained in comparative example 2(a) and example 2(b) after being soaked in the simulated body fluid for 4 weeks, respectively.
Fig. 5 is a micro-CT image of induced bioactive 3D printed ceramic SD rat skull defect implanted for 12 weeks according to the present invention, wherein (a) and (e) are comparative examples 2, (b) and (f) are examples 2, (c) and (g) are examples 4, and (D) is example 5.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the components and amounts of the photosensitive resin premix used were: 75 parts of 1, 6-hexanediol diacrylate, 22 parts of pentaerythritol triacrylate, 1 part of 4, 4-bis (diethoxy) benzophenone and 2 parts of a dispersant with the brand number of R1100.
The particle size of the decalcified bone matrix adopted in the following embodiment is 100-900 μm; the particle size of the calcium silicate is less than 10 mu m.
Comparative example 1
A3D printing biological ceramic is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the obtained ceramic slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see a model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2m) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1100 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket; tests show that the compressive strength of the obtained ceramic bracket is 16 +/-2 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Comparative example 2
A3D printing biological ceramic is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the obtained ceramic slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see a model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2m) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1200 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket; tests show that the compressive strength of the obtained ceramic bracket is 22 +/-3 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Example 1
An inducible bioactive 3D printing ceramic, which is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the obtained ceramic slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see a model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2m) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time of 10s, spreadThe thickness of the material is 10 mu m) to ensure that the ceramic slurry is piled up and overlapped layer by layer for forming, and the uncured slurry is cleaned off to obtain a ceramic bracket biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1100 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket;
4) mixing calcium sulfate hemihydrate with water according to the proportion of 1g/0.30mL to prepare calcium sulfate-based repair slurry, dipping 3D printed calcium silicate ceramic into the obtained calcium sulfate-based repair slurry, and performing ultrasonic treatment to fully fill the slurry into pores of the bracket;
5) and taking out a sample, removing redundant slurry on the surface, curing at normal temperature for 24h, and drying at 60 ℃ to constant weight to obtain the inducible bioactive 3D printing ceramic.
The compressive strength of the inducible bioactive 3D printing ceramic obtained in the embodiment is 20 +/-3 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Example 2
An inducible bioactive 3D printing ceramic, which is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the obtained ceramic slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see a model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2mm) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1200 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket;
4) mixing calcium sulfate hemihydrate with water according to the proportion of 1g/0.30mL to prepare calcium sulfate-based repair slurry, dipping 3D printed calcium silicate ceramic into the obtained calcium sulfate-based repair slurry, and performing ultrasonic treatment to fully fill the slurry into pores of the bracket;
5) taking out a sample, removing redundant slurry on the surface, curing at normal temperature for 24h, and drying at 60 ℃ to constant weight to obtain bioactive 3D printing bioceramic; tests prove that the compressive strength of the inducible bioactive 3D printing ceramic obtained in the embodiment is 28 +/-3 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Example 3
An inducible bioactive 3D printing ceramic, which is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the obtained ceramic slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see a model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2mm) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1200 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket;
4) mixing calcium sulfate hemihydrate and water according to the proportion of 1g/0.3mL to form slurry, putting the 3D printed calcium silicate ceramic bracket into the slurry, and filling the slurry into the pores of the bracket through ultrasonic treatment;
5) and taking out a sample, filling the decalcified bone matrix into a pore with the pore diameter of 2mm, removing redundant slurry on the surface, curing at normal temperature for 24 hours, and freeze-drying to obtain the inducible bioactive 3D printing bioceramic.
The ceramic obtained in the example has the compression strength of 28 plus or minus 4MPa and the total heavy metal content (calculated by lead) of less than 50 ppm.
Example 4
An inducible bioactive 3D printing ceramic, which is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix, and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see the model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2mm) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1200 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the 3D printing calcium silicate ceramic bracket;
4) mixing a compound of 99.8 parts of calcium sulfate hemihydrate and 0.2 part of deferoxamine with water according to the proportion of 1g/0.30mL to prepare calcium sulfate-based repair slurry, dipping 3D printed calcium silicate ceramic into the obtained calcium sulfate-based repair slurry, and performing ultrasonic treatment to fully fill the slurry into pores of the bracket;
5) and taking out a sample, removing redundant slurry on the surface, curing at normal temperature for 24h, and drying at 60 ℃ to constant weight to obtain the inducible bioactive 3D printing bioceramic.
According to a test formula, the compressive strength of the ceramic obtained in the embodiment is 28 +/-3 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Example 5
An inducible bioactive 3D printing ceramic, which is prepared by the following steps:
1) preparing ceramic slurry: adding 78 parts by mass of calcium silicate powder into 22 parts by mass of photosensitive resin premix (treatment amount), and stirring at normal pressure to uniformly disperse the components to obtain ceramic slurry;
2) printing and forming: pouring the slurry into a charging basket of a three-dimensional photocuring forming printer, introducing an STL format model (see the model corresponding to the model in figure 2 in figure 1, wherein the size of a large hole is 2mm, the size of a small hole is 0.5mm, and the thickness is 2mm) into the three-dimensional photocuring forming printer, and adjusting photocuring printing parameters (the exposure intensity is 800 mw/cm)2Exposure time is 10s, and spreading thickness is 10 mu m) to enable the ceramic slurry to be stacked and formed layer by layer, and washing the uncured slurry to obtain a ceramic support biscuit;
3) placing the ceramic support biscuit in a muffle furnace for degreasing sintering, wherein the degreasing sintering system is as follows: firstly, heating from 30 ℃ to 300 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then increasing the temperature to 600 ℃ at the rate of 5 ℃/min, preserving the heat for 2 hours, then increasing the temperature to 1200 ℃ at the rate of 3 ℃/min, preserving the heat for 2 hours, and finally, spontaneously combusting and cooling to room temperature to obtain the porous 3D printing calcium silicate ceramic bracket;
4) mixing a compound of 99.8 parts of calcium sulfate hemihydrate and 0.2 part of deferoxamine with water according to the proportion of 1g/0.30mL to prepare calcium sulfate-based repair slurry, dipping 3D printed calcium silicate ceramic into the obtained calcium sulfate-based repair slurry, and performing ultrasonic treatment to fully fill the slurry into pores of the bracket;
5) and taking out a sample, removing redundant slurry on the surface, curing at normal temperature for 24h, and drying at 60 ℃ to constant weight to obtain the inducible bioactive 3D printing bioceramic.
According to a test formula, the compressive strength of the ceramic obtained in the embodiment is 26 +/-3 MPa, and the total amount of heavy metals (calculated by lead) is less than 50 ppm.
Fig. 1 is a topography of the porous 3D printed calcium silicate ceramic scaffold of the present invention, which shows that a sample can be prepared into a more complex form by a 3D printing technology, and personalized customization can be realized by combining technologies such as CT and nuclear magnetic resonance.
Fig. 2 is a topography of a 3D printed bioceramic obtained by filling a calcium sulfate-based repair slurry into a porous 3D printed calcium silicate ceramic scaffold and curing (and removing calcium sulfate-based components in macropores).
Fig. 3 is an XRD pattern of the 3D printed ceramics obtained in comparative example 2(a) and example 2, in which (a) has peaks characteristic to calcium silicate and (b) has peaks characteristic to calcium silicate, calcium sulfate hemihydrate and calcium sulfate dihydrate without other impurity peaks.
FIG. 4 is an SEM image (b) of the 3D printed ceramics obtained in comparative example 2(a) and example 2(b) after being soaked in simulated body fluid for 4 weeks, respectively, and it can be seen that the ceramic surface has many micro-porous structures; after the bone is soaked in the simulated body fluid, a large amount of granular hydroxyapatite is formed on the surface, which is beneficial to the adhesion of osteoblasts and accelerates the healing of bones.
FIG. 5 is a 12-week micro-CT image of a bioactive 3D printed ceramic SD rat cranial defect implant according to the present invention, wherein (a) and (e) are comparative examples 2, (b) and (f) are examples 2, (c) and (g) are examples 4, and (D) is example 5; in the figures, (a), (b), (c) and (d) are all degraded to a certain degree, (a) a surface mineralized layer is not formed, (b), (c) and (d) surface mineralized layers are formed, and (c) and (d) have better bone formation effects, which show that the mineralization capability of calcium silicate can be obviously improved by introducing calcium sulfate into a calcium silicate-based ceramic structure, the bone formation capability of the material can be improved by desferrioxamine, and the DBM can enable the material to form bone, so that the bone defect can be rapidly healed; (g) compared with the vascularization effect of (e) and (f), the deferoxamine can promote vascularization and thus promote osteogenesis.
The ceramic provided by the invention can realize the preparation of a bionic structure through a 3D printing technology, and can realize clinical customization according to the state of illness of a patient, so that the pain of the patient is relieved, and the prepared ceramic has high mechanical strength and plays a certain role in mechanical support. In the degradation process, calcium sulfate is preferentially degraded to form a local slightly acidic environment, so that the release of an induction factor is accelerated, and meanwhile, hydroxyapatite is formed on the surface of the material, so that the adhesion of osteoblasts is facilitated, and the growth of bones is promoted.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (10)

1. An inducible bioactive 3D printing ceramic is characterized in that a porous 3D printing calcium silicate ceramic bracket is immersed in calcium sulfate-based repair slurry and is solidified and freeze-dried to form the ceramic; the 3D printing calcium silicate ceramic support is formed by preparing ceramic slurry from calcium silicate powder and photosensitive resin premixed liquid, and then carrying out photocuring 3D printing and degreasing sintering according to a design model.
2. The inducible bioactive 3D printed ceramic of claim 1, wherein the decalcified bone matrix is further introduced into the porous 3D printed calcium silicate ceramic scaffold filled with the calcium sulfate-based repair slurry prior to curing, freeze-drying.
3. The inducible bioactive 3D printing ceramic of claim 1, comprising a macro-pore and a micro-pore structure, wherein the micro-pore size is 400-1000 μm and the macro-pore size is 2-5 mm.
4. The inducible bioactive 3D printing ceramic of claim 1 wherein the calcium sulfate-based repair slurry is a water-based slurry of calcium sulfate-based repair components, wherein the solid-to-liquid ratio of calcium sulfate-based repair components to water is 1g: 0.23-0.50 mL.
5. The inducible bioactive 3D printing ceramic of claim 1 wherein the calcium sulfate-based repair component is calcium sulfate hemihydrate or a complex thereof with a functional component; wherein the content of the calcium sulfate hemihydrate is 95-99.9 wt%.
6. The inducible bioactive 3D printing ceramic of claim 1 wherein the functional component is an antibiotic, deferoxamine, magnesium or strontium salt.
7. The inducible bioactive 3D printing ceramic of claim 2 wherein the demineralized bone matrix has a particle size of 100 to 900 μm; the particle size of the calcium silicate is less than 10 mu m.
8. The method for preparing the inducible bioactive 3D printing ceramic according to claims 1 to 7, comprising the following steps:
1) adding calcium silicate powder into the photosensitive resin premix, and uniformly mixing under normal pressure to obtain ceramic slurry;
2) adding the ceramic slurry obtained in the step 1) into a three-dimensional photocuring forming printer;
3) creating a porous model by using three-dimensional modeling software, and introducing the porous model into a three-dimensional photocuring molding printer;
4) adjusting photocuring printing parameters to enable the ceramic slurry to be stacked and formed layer by layer, and cleaning the uncured slurry to obtain a ceramic support biscuit;
5) placing the obtained ceramic support biscuit in a muffle furnace for degreasing and sintering to obtain a 3D printed calcium silicate ceramic support;
6) uniformly mixing the calcium sulfate-based repair component with water in proportion to prepare calcium sulfate-based repair slurry;
8) putting the obtained 3D printed calcium silicate ceramic bracket into the obtained calcium sulfate-based repair slurry, and stirring or ultrasonically treating to ensure that the calcium sulfate-based repair slurry is fully filled into the pore channel structure of the bracket;
9) introducing the decalcified bone matrix into the macroporous pores filled with the calcium sulfate-based repair slurry, curing at normal temperature, and freeze-drying to obtain the inducible bioactive 3D printing bioceramic.
9. The preparation method according to claim 1, wherein the mass ratio of the calcium silicate powder to the photosensitive resin premix is 60-80: 20-40.
10. The method according to claim 1, wherein the degreasing sintering schedule is set as follows: firstly, heating to 250-350 ℃ at the speed of 0.5-10 ℃/min, and preserving heat for 2-3 h; then heating to 550-650 ℃ at the speed of 0.5-10 ℃/min, and preserving heat for 2-3 h; heating to the sintering temperature at the speed of 2-5 ℃/min, preserving the heat for 2-3 h, and finally naturally cooling to the room temperature; wherein the sintering temperature is 1100-1200 ℃.
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