CN115105644A - 3D printing artificial bone repair material and preparation method thereof - Google Patents
3D printing artificial bone repair material and preparation method thereof Download PDFInfo
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- CN115105644A CN115105644A CN202210845204.XA CN202210845204A CN115105644A CN 115105644 A CN115105644 A CN 115105644A CN 202210845204 A CN202210845204 A CN 202210845204A CN 115105644 A CN115105644 A CN 115105644A
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 230000008439 repair process Effects 0.000 title claims abstract description 69
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 67
- 238000010146 3D printing Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012876 carrier material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 239000004132 Calcium polyphosphate Substances 0.000 claims description 10
- 235000019827 calcium polyphosphate Nutrition 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000009474 hot melt extrusion Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000035755 proliferation Effects 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000011164 ossification Effects 0.000 abstract description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000004069 differentiation Effects 0.000 abstract description 3
- 210000000963 osteoblast Anatomy 0.000 abstract description 3
- 210000002997 osteoclast Anatomy 0.000 abstract description 3
- 238000007792 addition Methods 0.000 description 5
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- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002054 transplantation Methods 0.000 description 2
- 206010018852 Haematoma Diseases 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000010072 bone remodeling Effects 0.000 description 1
- 230000022159 cartilage development Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000537 nasal bone Anatomy 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000002138 osteoinductive effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100001055 skeletal defect Toxicity 0.000 description 1
- 210000003625 skull Anatomy 0.000 description 1
- CIOAGBVUUVVLOB-AKLPVKDBSA-N strontium-91 Chemical compound [91Sr] CIOAGBVUUVVLOB-AKLPVKDBSA-N 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
Abstract
The invention provides a 3D printing artificial bone repair material and a preparation method thereof, wherein the repair material is formed by compounding a nano-doped bone repair material and a water-based degradable carrier material, and the nano-doped bone repair material is formed by compounding nano-hydroxyapatite doped with strontium carbonate and nano-titanium powder; on the basis of conventional hydroxyapatite, the nanometer doped bone repair material is also doped with strontium element and nanometer titanium at high temperature, and the strontium can inhibit the activity and proliferation of osteoclast in an organism so as to inhibit bone absorption, so that the addition of the strontium can accelerate the differentiation of osteoblast and promote the proliferation of preosteoblast so as to accelerate the osteogenesis process, and the addition of the nanometer titanium further improves the printed integral strength of the repair material.
Description
Technical Field
The invention belongs to the technical field of artificial bone repair, and relates to a 3D printing artificial bone repair material and a preparation method thereof.
Background
Bone tissue is the largest tissue organ in the human body, which is important for life activities, and at the same time, it is the most vulnerable tissue organ. At present, the injury rate of skull, frontal face bone, nasal bone and phalanx caused by accidents such as traffic accidents, high-altitude falling and the like in the world is higher and higher, and the skeletal defects caused by genetic reasons also occur. The process of bone repair is very lengthy and mainly includes a hematoma and inflammation phase, an initial callus response phase, a chondrogenesis phase, and a bone formation and remodeling phase. In the bone repair process, the normal life of the patient is greatly influenced, and the patient and family members thereof are subjected to heavy psychological burden.
The shape and function of a defect part are usually restored through bone transplantation, repair and reconstruction surgery clinically, the bone transplantation becomes the graft with the largest demand next to blood transfusion, and the demand is increasing year by year. Therefore, the artificial bone repair material attracts attention, and is widely used for filling local gaps generated on human bones so as to achieve the aim of bone repair.
The ideal artificial bone repair material needs to have excellent biocompatibility, osteoconductivity and osteoinductivity, can be made for normal cell activities, can provide space for the growth of new tissues and be gradually replaced by the new tissues, and also needs to have certain mechanical properties, can bear the stress in the operation process and the bone growth process, and in addition, the material also needs to have a coherent porous structure to transport nutrients and wastes for the generation of the new tissues, however, the existing artificial bone repair material generally has the defects that the mechanical properties, the biocompatibility and the osteoinductive capacity need to be further improved.
Disclosure of Invention
The invention aims to provide a 3D printing artificial bone repair material and a preparation method thereof, and aims to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
the 3D printing artificial bone repair material is formed by compounding a nano-doped bone repair material and a water-based degradable carrier material, wherein the nano-doped bone repair material is formed by compounding nano-hydroxyapatite doped with strontium carbonate and nano-titanium powder.
In the 3D printing artificial bone repair material and the preparation method thereof, the aqueous degradable carrier material consists of DL-lactide, glycolide and polyethylene glycol.
In the 3D printing artificial bone repair material and the preparation method thereof, in the aqueous degradable carrier material, the mass proportion content of DL-lactide is 20-30%, the mass proportion content of glycolide is 10-40%, and the mass proportion content of polyethylene glycol is 40-50%.
In the 3D printing artificial bone repair material and the preparation method thereof, in the nano doped bone repair material, the mass content of nano hydroxyapatite is 90-99%, the mass content of strontium carbonate is 2-6%, and the mass content of nano titanium powder is 1-3%.
A preparation method of a 3D printing artificial bone repair material is used for preparing the artificial bone repair material, and comprises the following specific steps:
the method comprises the following steps: respectively weighing strontium carbonate and nano-hydroxyapatite in corresponding mass proportion, placing the mixed salt in a crucible, calcining for 12 hours at a constant temperature of 500 ℃, then gradually heating to 1200 ℃ at a heating rate of 30 ℃/min, melting the mixed salt, then preserving heat for 2 hours, and then quenching to obtain a strontium-doped calcium polyphosphate amorphous sintering material;
step two: grinding the strontium-doped calcium polyphosphate amorphous sintering material, sieving with a 200-mesh sieve, adding nano titanium powder, mixing, performing secondary high-temperature calcination, and then crushing and grinding the sintering material to obtain a nano doped-based bone repair material;
step three: weighing 5g of DL-lactide, glycolide and polyethylene glycol in a certain mass ratio, mixing with 20mL of distilled water, placing in a refrigerator at 4 ℃, stirring for 30min every 24 h, obtaining an aqueous degradable carrier material suspension after 3d, then adding the nano-doped bone repair material according to the ratio of 20:70, and mixing the nano-doped bone repair material with the suspension to obtain a repair material;
step four: after the materials are uniformly mixed, freeze-drying is carried out, then solid particles are crushed to form small particles with the particle size less than or equal to 2mm, and finally the small particles are extruded into uniform linear materials with the diameters of 1-3 mm and capable of being printed by 3D through hot-melt extrusion equipment to be printed by 3D.
Compared with the prior art, the 3D printing artificial bone repair material and the preparation method thereof have the advantages that:
1. the high molecular water-based degradable carrier material is prepared by DL-lactide, glycolide and polyethylene glycol, can be used as a curing liquid, can play a role of slowly releasing the nano doped base bone repair material in vivo, can slowly release Ca and P ions and induce the formation of new bone tissues, can overcome the defect that the conventional TCP powder needs sintering molding, can be dissolved in water to form free flowing liquid when the temperature is lower than the phase transition temperature, and can form a gel shape when the temperature is increased to be higher than the phase transition temperature, the water solution of the polymer is reversible in the gel forming process, so that the high molecular water-based degradable carrier material is a good adhesive material, the repair material prepared by mixing can improve the hardness of TCP and increase the elasticity of the material, meanwhile, the 3D printing technology can be used for rapidly preparing the personalized entity, and the method for preparing the artificial bone by combining the nano doped base bone repair material and the 3D printing technology has the advantages of simplicity and easy implementation, can meet the characteristic of rapid preparation in large batch.
2. The nanometer doped bone repair material is doped with strontium element and nanometer titanium at high temperature on the basis of conventional hydroxyapatite, strontium can inhibit the activity and proliferation of osteoclast in a body so as to inhibit bone absorption, so that the addition of strontium can accelerate the differentiation of osteoblast and promote the proliferation of preosteoblast so as to accelerate the osteogenesis process, and the addition of nanometer titanium further improves the printed integral strength of the repair material.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
The first embodiment is as follows:
the preparation method comprises the following specific steps:
the method comprises the following steps: respectively weighing 2 mass percent of strontium carbonate and 97 mass percent of nano-hydroxyapatite, placing the mixed salt in a crucible, calcining for 12 hours at a constant temperature of 500 ℃, gradually heating to 1200 ℃ at a heating rate of 30 ℃/min, melting the mixed salt, keeping the temperature for 2 hours, and then quenching to obtain the strontium-doped calcium polyphosphate amorphous sintering material;
step two: grinding the strontium-doped calcium polyphosphate amorphous sintering material, sieving with a 200-mesh sieve, adding 1% of nano titanium powder, mixing, performing secondary high-temperature calcination, and then crushing and grinding the sintering material to obtain a nano doped base bone repair material;
step three: weighing 5g of DL-lactide, glycolide and polyethylene glycol in a certain mass ratio, mixing with 20mL of distilled water, placing in a refrigerator at 4 ℃, stirring for 30min every 24 h, obtaining an aqueous degradable carrier material suspension after 3d, then adding the nano-doped bone repair material according to the ratio of 20:70, and mixing the nano-doped bone repair material with the suspension to obtain a repair material;
wherein, the mass proportion content of DL-lactide is 20-30%, the mass proportion content of glycolide is 10-40%, and the mass proportion content of polyethylene glycol is 40-50%;
step four: after the materials are uniformly mixed, freeze-drying is carried out, then solid particles are crushed to form small particles with the particle size being less than or equal to 2mm, and finally the small particles are extruded into uniform linear materials with the diameters of 1-3 mm and capable of being printed by 3D through hot-melt extrusion equipment to be printed by 3D.
Example two:
the preparation method comprises the following specific steps:
the method comprises the following steps: respectively weighing strontium carbonate with the mass ratio of 4% and nano-hydroxyapatite with the mass ratio of 94%, placing the mixed salt in a crucible, calcining for 12 hours at the constant temperature of 500 ℃, then gradually heating to 1200 ℃ at the heating rate of 30 ℃/min, melting the mixed salt, then keeping the temperature for 2 hours, and then quenching to obtain the strontium-doped calcium polyphosphate amorphous sintering material;
step two: grinding the strontium-doped calcium polyphosphate amorphous sintering material, sieving with a 200-mesh sieve, adding 2% of nano titanium powder, mixing, performing secondary high-temperature calcination, and then crushing and grinding the sintering material to obtain a nano doped base bone repair material;
step three: weighing 5g of DL-lactide, glycolide and polyethylene glycol in a certain mass ratio, mixing with 20mL of distilled water, placing in a refrigerator at 4 ℃, stirring for 30min every 24 h, obtaining an aqueous degradable carrier material suspension after 3d, then adding the nano-doped bone repair material according to the ratio of 20:70, and mixing the nano-doped bone repair material with the suspension to obtain a repair material;
wherein, the mass proportion content of DL-lactide is 20-30%, the mass proportion content of glycolide is 10-40%, and the mass proportion content of polyethylene glycol is 40-50%;
step four: after the materials are uniformly mixed, freeze-drying is carried out, then solid particles are crushed to form small particles with the particle size less than or equal to 2mm, and finally the small particles are extruded into uniform linear materials with the diameters of 1-3 mm and capable of being printed by 3D through hot-melt extrusion equipment to be printed by 3D.
Example three:
the preparation method comprises the following specific steps:
the method comprises the following steps: respectively weighing 6 mass percent of strontium carbonate and 91 mass percent of nano-hydroxyapatite, placing the mixed salt in a crucible, calcining for 12 hours at a constant temperature of 500 ℃, gradually heating to 1200 ℃ at a heating rate of 30 ℃/min, melting the mixed salt, keeping the temperature for 2 hours, and then quenching to obtain the strontium-doped calcium polyphosphate amorphous sintering material;
step two: grinding the strontium-doped calcium polyphosphate amorphous sintering material, sieving with a 200-mesh sieve, adding 3% of nano titanium powder, mixing, performing secondary high-temperature calcination, and then crushing and grinding the sintering material to obtain a nano doped base bone repair material;
step three: weighing 5g of DL-lactide, glycolide and polyethylene glycol in a certain mass ratio, mixing with 20mL of distilled water, placing in a refrigerator at 4 ℃, stirring for 30min every 24 h, obtaining an aqueous degradable carrier material suspension after 3d, then adding the nano-doped bone repair material according to the ratio of 20:70, and mixing the nano-doped bone repair material with the suspension to obtain a repair material;
wherein, the mass proportion content of DL-lactide is 20-30%, the mass proportion content of glycolide is 10-40%, and the mass proportion content of polyethylene glycol is 40-50%;
step four: after the materials are uniformly mixed, freeze-drying is carried out, then solid particles are crushed to form small particles with the particle size less than or equal to 2mm, and finally the small particles are extruded into uniform linear materials with the diameters of 1-3 mm and capable of being printed by 3D through hot-melt extrusion equipment to be printed by 3D.
The invention relates to a 3D printing artificial bone repair material and a preparation method thereof, wherein a high molecular aqueous degradable carrier material is prepared by DL-lactide, glycolide and polyethylene glycol, can be used as a curing liquid, can play a role of slowly releasing a nano doping base bone repair material in vivo, can slowly release Ca and P ions and induce to form new bone tissues, can overcome the defect that the conventional TCP powder needs sintering molding, when the temperature is lower than the phase transition temperature, the polymer can be dissolved in water to form free flowing liquid, and when the temperature is increased to be higher than the phase transition temperature, the aqueous solution of the polymer forms a gel shape, the gel forming process is reversible, the gel is a good adhesive material, the repair material prepared by mixing can improve the hardness of TCP and increase the elasticity of the material, and meanwhile, the 3D printing technology can be rapidly prepared aiming at personalized entities, the method for preparing the artificial bone by combining the nano-doped bone repair material and the 3D printing technology has the advantages of simplicity and feasibility, and can meet the requirement of large-scale and rapid preparation, the nano-doped bone repair material is doped with strontium element and nano-titanium at high temperature on the basis of conventional hydroxyapatite, and the strontium can inhibit the activity and proliferation of osteoclasts in a body so as to inhibit bone absorption, so that the addition of the strontium can accelerate the differentiation of osteoblasts and promote the proliferation of preosteoblasts so as to accelerate the osteogenesis process, and the addition of the nano-titanium further improves the printed integral strength of the repair material.
Those not described in detail in this specification are within the skill of the art. The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (5)
1. The 3D printing artificial bone repair material is characterized in that the repair material is formed by compounding a nano-doped bone repair material and a water-based degradable carrier material, and the nano-doped bone repair material is formed by compounding nano-hydroxyapatite doped with strontium carbonate and nano-titanium powder.
2. The 3D printing artificial bone repair material and the preparation method thereof according to claim 1, characterized in that the aqueous degradable carrier material is composed of DL-lactide, glycolide and polyethylene glycol.
3. The 3D printing artificial bone repair material and the preparation method thereof according to claim 2, characterized in that in the aqueous degradable carrier material, the mass ratio content of DL-lactide is 20-30%, the mass ratio content of glycolide is 10-40%, and the mass ratio content of polyethylene glycol is 40-50%.
4. The 3D printing artificial bone repair material and the preparation method thereof according to claim 1, characterized in that in the nano-doped bone repair material, the mass content of nano-hydroxyapatite is 90-99%, the mass content of strontium carbonate is 2-6%, and the mass content of nano-titanium powder is 1-3%.
5. A preparation method of 3D printing artificial bone repair material, which is used for preparing the artificial bone repair material of any one of claims 1-4, and is characterized by comprising the following specific steps:
the method comprises the following steps: respectively weighing strontium carbonate and nano-hydroxyapatite in corresponding mass proportion, placing the mixed salt in a crucible, calcining for 12 hours at a constant temperature of 500 ℃, then gradually heating to 1200 ℃ at a heating rate of 30 ℃/min, melting the mixed salt, then preserving heat for 2 hours, and then quenching to obtain a strontium-doped calcium polyphosphate amorphous sintering material;
step two: grinding the strontium-doped calcium polyphosphate amorphous sintering material, sieving with a 200-mesh sieve, adding nano titanium powder, mixing, performing secondary high-temperature calcination, and then crushing and grinding the sintering material to obtain a nano doped-based bone repair material;
step three: weighing 5g of DL-lactide, glycolide and polyethylene glycol in a certain mass ratio, mixing with 20mL of distilled water, placing in a refrigerator at 4 ℃, stirring for 30min every 24 h, obtaining an aqueous degradable carrier material suspension after 3d, then adding the nano-doped bone repair material according to the ratio of 20:70, and mixing the nano-doped bone repair material with the suspension to obtain a repair material;
step four: after the materials are uniformly mixed, freeze-drying is carried out, then solid particles are crushed to form small particles with the particle size less than or equal to 2mm, and finally the small particles are extruded into uniform linear materials with the diameters of 1-3 mm and capable of being printed by 3D through hot-melt extrusion equipment to be printed by 3D.
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CN107929807A (en) * | 2017-11-28 | 2018-04-20 | 东华大学 | The compound polycaprolactone material of strontium-doped hydroxyapatite and its preparation and application |
CN110982335A (en) * | 2019-12-30 | 2020-04-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self-curing hydroxyapatite 3D printing ink |
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