CN105381505A - 3D printing preparation method of bond defect repair stent - Google Patents

3D printing preparation method of bond defect repair stent Download PDF

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Publication number
CN105381505A
CN105381505A CN201510836310.1A CN201510836310A CN105381505A CN 105381505 A CN105381505 A CN 105381505A CN 201510836310 A CN201510836310 A CN 201510836310A CN 105381505 A CN105381505 A CN 105381505A
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bone
defect repair
bone defect
silicon
repair support
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王红
张楠
张莉
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QINGDAO UNIQUE PRODUCTS DEVELOP CO Ltd
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QINGDAO UNIQUE PRODUCTS DEVELOP CO Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/425Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/08Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a 3D printing preparation method of a bone defect repair stent. The method comprises the following steps: taking calcium phosphate bone cement and calcium-containing mesoporous silicon as raw materials, mixing, and grinding to obtain calcium phosphorus silicon-based active bone repair material powder; and then uniformly mixing the calcium phosphorus silicon-based active bone repair material powder with curing liquid, and constructing the obtained mixture to obtain the bone defect repair stent by virtue of a 3D printing rapid prototyping method. The bone repair material stent is prepared by virtue of the 3D printing method, so that the shape, the structure and the porosity of the stent can be accurately controlled, and the cell attachment proliferation can be facilitated; and meanwhile, the selected calcium phosphorus silicon-based active bone repair material has good biological activity and bone forming effect and is suitable for being used as a novel bone defect repair stent.

Description

A kind of 3D printing preparation method of bone defect repair support
Technical field
The invention belongs to tissue engineering technique field, be specially adapted to the preparation of biomedical tissue engineering scaffold material, be specially the 3D printing preparation method of new multistage micro structure calcium phosphorus silicon-based active bone renovating material support.
Background technology
The osseous tissue defect caused because of factors such as wound, infection, tumor, congenital malformations brings huge inconvenience to the life of patient.Bone collection is the conventional treatment means solving Cranial defect problem.It is good that autologous bone transplanting has curative effect, without the advantage of immunogenicity, but, because the autologous bone amount for transplanting is limited, for the damage in bone district for patient brings more misery.Allogenic bone transplantation is limited to Human immune responses, and is attended by pathophorous risk.Bone repairing support as the important research content of bone tissue engineer, for bone defect healing brings new hope.From the angle of osseous tissue self-healing, desirable tissue scaffold design needs to have outside good biocompatibility, biological degradability, also needs the complex appearance having 3 D stereo loose structure and match with defect.Only have this structure just to have higher specific surface area and space, be beneficial to the load of active factors, cell adhesion growth, extrtacellular matrix deposition, nutrition and oxygen enters and metabolite is discharged, be also conducive to blood vessel and neural etc. growing into.In addition, provide support until cambium has own biological mechanical characteristic because support is required to be cambium, visible, plasticity and good mechanical strength are also weigh a large important indicator of tissue scaffold design performance quality.Although the advantage that traditional method preparing porous support materials is had nothing in common with each other, be manual operation, poor repeatability; There is potential toxic and side effects in perforating agent; Lack the control to pore structure (size, space trend, connectedness etc. as hole), more lack the ability manufacturing complex appearance.The one that the eighties in 20th century occurs is based on computer-aided design (Computeraideddesign, CAD) new manufacture---rapid shaping (Rapidprototyping, RP) technology, have and manufacture individuation and one-time formed feature, can design and controlled synthesis pore passage structure, construct the 3D solid of any complicated shape, for the profiling of tissue engineering bracket and bionical manufacture provide a new way.
Summary of the invention
The object of the invention is for solving Cranial defect problem, a kind of 3D printing preparation method of bone defect repair support is provided, use calcic mesoporous silicon material, adopt speed forming method, build the new multistage micro structure calcium phosphorus silicon-based active bone renovating material support with different pore passage structure.
A 3D printing preparation method for bone defect repair support, is characterized in that, with calcium phosphate bone cement, calcic mesoporous silicon for raw material mixed grinding, and obtained calcium phosphorus silicon-based active bone renovating material powder; Mix homogeneously with consolidation liquid again, print speed forming method structure by 3D and obtain bone defect repair support.
Further, Li Jing≤50 μm of described calcium phosphate bone cement.
Further, in described calcium phosphorus silicon-based active bone renovating material, the mass ratio of calcium phosphate bone cement and calcic mesoporous silicon is 50-90:50-10.
Further, the mass ratio of described calcium phosphorus silicon-based active bone renovating material and consolidation liquid is 1:0.1-1.0.
Further, the preparation method of described calcic mesoporous silicon is in acid condition, and with polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer for template, silicon source and four water-calcium nitrate carry out that hydro-thermal reaction prepares.
Further, described silicon source is sodium silicate, Ludox, ethyl orthosilicate or sodium silicate.
Further, described hydrothermal temperature is 100-120 DEG C, and the response time is 40-50h.
Further, described silicon source is ethyl orthosilicate, and the mass ratio of described ethyl orthosilicate and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer is 2-3:1.
Further, in described calcic mesoporous silicon material, calcium, silicon mol ratio are 0.5-2:1.
The 3D printing preparation method of a kind of bone defect repair support of the present invention, the preparation method of described consolidation liquid is joined in polyvinyl alcohol water solution to be stirred to by sodium alginate to be uniformly dispersed, and obtains the poly-vinyl alcohol solution containing sodium alginate; Described is 1%-5% containing the mass fraction of sodium alginate in the poly-vinyl alcohol solution of sodium alginate.
Compared with prior art, advantage of the present invention and good effect are: the present invention prepares calcium phosphorus silicon-based active bone renovating material support by using the method for 3D printing, there is controlled pore passage structure and profile, can grow into for the tissue of support and optimal permeability is provided, and optimize the mechanical property of regenerating tissues.The present invention is printed by 3D and prepares bone renovating material support, by the form, structure, the porosity that arrange different printer models, different print parameters (as parameters such as print speed, feeding speed, needle diameter) accurately can control support, be beneficial to cell attachment propagation, the calcium phosphorus silicon-based active bone renovating material simultaneously selected has good biological activity and skeletonization effect, is suitable as a kind of novel bone defect repair support.
Accompanying drawing explanation
Fig. 1. the section picture of bone defect repair support prepared by the present invention;
Fig. 2. in figure, (A) is the design drawing of bone defect repair support model, in figure, (B, C) is axonometric chart and the top view of bone defect repair support prepared by the present invention, and in figure, (D, E, F) is the electron-microscope scanning figure of the bone defect repair support that the present invention prepares;
Fig. 3. take out sample tissue figure after stenter to implant 8 weeks, in figure (a, b) be respectively support HE dye 20 ×, 100 ×.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme of the present invention is described in further detail.
A kind of 3D printing preparation method of bone defect repair support, with calcium phosphate bone cement, calcic mesoporous silicon for raw material mixed grinding, be ground to Li Jing≤50 μm, obtained calcium phosphorus silicon-based active bone renovating material powder, mix homogeneously with consolidation liquid again, print speed forming method structure by 3D and obtain structure diversification, there is controlled pore passage structure and the bone defect repair support of profile.
Described calcium phosphate bone cement have can random-shaping, osteoconductive potential strong and can quick-setting characteristic; For preventing spray nozzle clogging, Li Jing≤50 μm of described calcium phosphate bone cement, can smoothly by nozzle molding that diameter is 0.52mm.In described calcium phosphorus silicon-based active bone renovating material, the mass ratio of calcium phosphate bone cement and calcic mesoporous silicon is 50-90:50-10.The mass ratio of described calcium phosphorus silicon-based active bone renovating material and consolidation liquid is 1:0.1-1.
Described calcic mesoporous silicon has good biological activity and degradability, preparation method is in acid condition, with polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 for template, silicon source and four water-calcium nitrate carry out that hydro-thermal reaction prepares, and in calcic mesoporous silicon material, calcium, silicon mol ratio are 0.5-2:1.Described silicon source is sodium silicate, Ludox, ethyl orthosilicate or sodium silicate, is preferably ethyl orthosilicate TEOS in the present invention.Concrete steps are:
1) polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 is dissolved in hydrochloric acid solution stirs, until mixed liquor clarification.The concentration of described hydrochloric acid solution is 1-2mol/L, and the amount ratio of described P123 and hydrochloric acid solution is 1g:30-40mL.Dropwise be added drop-wise to by TEOS in above-mentioned mixed liquor, the mass ratio of described TEOS and P123 is 2-3:1; Until TEOS add completely and prehydrolysis 10-20min after, be dropwise added drop-wise in mixed liquor by four water-calcium nitrate, the calcium silicon mol ratio of described four water-calcium nitrate and TEOS is 0.5-2:1; At room temperature stirring 4-6h makes system be uniformly dispersed, and stops stirring, still aging 20-30h, makes macromolecular solution self-assemble in standing process form precipitation; Then be transferred to hydrothermal reaction kettle and carry out isothermal reaction, be precipitated, hydrothermal temperature is 100-120 DEG C, and the response time is 40-50h.Filtering-depositing, thoroughly cleans with deionized water, and vacuum drying obtains white powder at 50-60 DEG C.
2) by the powder dispersion of above-mentioned drying in deionized water, magnetic agitation is uniformly dispersed, add four water-calcium nitrate, after stirred at ambient temperature 1.5-2.5h, 100-120 DEG C of freeze-day with constant temperature 20-30h obtains powdered substance, and through the 580-620 DEG C of above-mentioned powder of sintering, heating rate is 1 DEG C/min, furnace cooling after insulation 5-6h, obtains the calcic mesoporous silicon material that calcium silicon mol ratio is 0.5-2:1.
Calcium source is added at twice in the preparation method of described calcic mesoporous silicon, it is the effect playing the marking that first time adds calcium source, form headspace in the material, step 1) in calcium source can be cleaned up through washed with de-ionized water, step 2) in add calcium source after, through oversintering formed rock-steady structure.
In the preparation method of above-mentioned calcic mesoporous silicon, hydrothermal temperature, time and sintering temperature, heating rate play key effect to mesoporous silicon material performance: along with the temperature of hydro-thermal reaction raises, sample average aperture increases, specific surface area first increases and then decreases; Along with the hydro-thermal reaction time increases, sample average aperture first increases and then decreases, specific surface area first reduces rear increase; Along with sintering temperature raises, sample average aperture reduces, and temperature is too high, and meso-hole structure subsides.
The preparation method of described consolidation liquid first prepares polyvinyl alcohol water solution, is to be dissolved in deionized water by polyvinyl alcohol white powder, is fully uniformly mixed under constant temperature oil bath 70-100 DEG C environment with magnetic stirring apparatus; Then sodium alginate is joined in polyvinyl alcohol water solution to be stirred to and be uniformly dispersed, obtain the poly-vinyl alcohol solution containing sodium alginate.Wherein the mass fraction of polyvinyl alcohol water solution is 6%-15%, and described is 1%-5% containing the mass fraction of sodium alginate in the poly-vinyl alcohol solution of sodium alginate.
The operation that described 3D prints speed forming method is specially: first obtain corresponding anatomy mathematical model, the stent model needed for structure according to the histoorgan defect feature of patient self; Then calcium phosphorus silicon-based active bone renovating material powder is mixed homogeneously with consolidation liquid, join in biological 3D printer barrel, being layering successively to be printed on is loaded with on the three-dimensional micromotion platform of sterilizing glass film plates, can form pore passage structure and the controlled bone defect repair support of profile by the printer model arranging support.The support printing speed forming method acquisition through 3D of the present invention has personalized precise dimensions, higher with the matching degree of sufferer.
Embodiment 1
The 3D printing preparation method of a kind of bone defect repair support of the present invention, comprises the following steps:
1) preparation of mesoporous silicon material: it is stir in the hydrochloric acid solution of 1.6mol/L that 4.0g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 is dissolved in 150mL concentration, until system clarification.The TEOS of 8.5g is dropwise added drop-wise in solution, until TEOS add completely and prehydrolysis 15min after, by amount, 2.6g four water-calcium nitrate is joined in solution, at room temperature stir after 5h makes system be uniformly dispersed and stop stirring, still aging 24h, is then transferred to hydrothermal reaction kettle 100 DEG C of isothermal reaction 48h and obtains precipitation.Filtering-depositing, thoroughly cleans with deionized water, and vacuum drying obtains white powder at 60 DEG C.By the powder dispersion of drying in 150mL deionized water, magnetic agitation is uniformly dispersed, add 2.6g four water-calcium nitrate, after stirred at ambient temperature 2h, 100 DEG C of freeze-day with constant temperature 24h, through 600 DEG C of above-mentioned powder of sintering, heating rate is 1 DEG C/min, furnace cooling after insulation 5h, obtains the calcic mesoporous silicon material that calcium silicon mol ratio is respectively 0.5:1.
2) preparation of consolidation liquid: take a certain amount of polyvinyl alcohol white powder, be dissolved in deionized water according to corresponding proportion, is fully uniformly mixed with magnetic stirring apparatus under constant temperature oil bath 80 DEG C of environment, and obtaining mass concentration is 10% poly-vinyl alcohol solution; Corresponding proportion sodium alginate powder is added by amount and by magnetic stirring apparatus high-speed stirred to being uniformly dispersed, obtaining is the poly-vinyl alcohol solution of 2% sodium alginate containing mass concentration in poly-vinyl alcohol solution.
3) 3D prints: by calcium phosphate bone cement and calcic mesoporous silicon powder, 50:50 mixed grinding is even in mass ratio, again with consolidation liquid in mass ratio 1:0.1 mix homogeneously, add in biometric print machine barrel, being layering successively to be printed on is loaded with on the three-dimensional micromotion platform of sterilizing glass film plates, is formed and has controlled pore passage structure and the bone defect repair support of profile.
4) rack forming: the preforming prepared is propped up and is placed on 37 DEG C, carry out hydration reaction 72h in 100% humidity environment, obtain end-product.
Be illustrated in figure 1 the section picture of bone defect repair support prepared by the present invention.As shown in Figure 2, in figure, (A) is the design drawing of the stent model constructed by the histoorgan defect feature of patient, in figure, (B, C) is the design drawing according to building in (A) in figure, the axonometric chart of the bone defect repair support prepared by the present invention and top view.In contrast design figure figure, in the axonometric chart of (A) and support and top view figure, (B, C) is visible, in kind and design drawing structure is basically identical.In figure, (D, E, F) is the electron-microscope scanning figure of the bone defect repair support that the present invention prepares, the longitudinal section of support is observed from (D, F) figure, visible gradient-structure support two parts X-Y direction has equally distributed intercommunicating pore, duct size is respectively 300 μm and about 500 μm, interlayer arrangement evenly, in conjunction with good, without division and collapse phenomenon.From figure, observe functionally gradient material (FGM) two parts junction section in E, can see that path changing does not affect the integrity of support, upper and lower two parts combine good.
The sample tissue figure taken out after being illustrated in figure 3 stenter to implant 8 weeks, in figure (a, b) be respectively support HE dye 20 ×, 100 ×, in figure, H represents host bone tissue, and M represents bone defect repair support of the present invention, and F represents fibrous tissue.Observe sample tissue, support aperture is inner and have abundant collagen tissue and blood capillary to grow into around, a large amount of osteoprogenitor cell can be observed in its inside, internal stent has no the formation of area of new bone, still be in the initial stage of skeletonization, implant site NIP reacts, and shows that bone defect repair support of the present invention has good histocompatibility.
Above embodiment is only a kind of in the several preferred implementation of the present invention, it should be pointed out that and the invention is not restricted to above-described embodiment; For the person of ordinary skill of the art, still the technical scheme described in previous embodiment can be modified, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.

Claims (10)

1. a 3D printing preparation method for bone defect repair support, is characterized in that, with calcium phosphate bone cement, calcic mesoporous silicon for raw material mixed grinding, and obtained calcium phosphorus silicon-based active bone renovating material powder; Mix homogeneously with consolidation liquid again, print speed forming method structure by 3D and obtain bone defect repair support.
2. the 3D printing preparation method of a kind of bone defect repair support according to claim 1, is characterized in that, Li Jing≤50 μm of described calcium phosphate bone cement.
3. the 3D printing preparation method of a kind of bone defect repair support according to claim 1, is characterized in that, in described calcium phosphorus silicon-based active bone renovating material, the mass ratio of calcium phosphate bone cement and calcic mesoporous silicon is 50-90:50-10.
4. the 3D printing preparation method of a kind of bone defect repair support according to claim 1, is characterized in that, the mass ratio of described calcium phosphorus silicon-based active bone renovating material and consolidation liquid is 1:0.1-1.0.
5. the 3D printing preparation method of a kind of bone defect repair support according to claim 1, it is characterized in that, the preparation method of described calcic mesoporous silicon is in acid condition, with polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer for template, silicon source and four water-calcium nitrate carry out that hydro-thermal reaction prepares.
6. the 3D printing preparation method of a kind of bone defect repair support according to claim 5, is characterized in that, described silicon source is sodium silicate, Ludox, ethyl orthosilicate or sodium silicate.
7. the 3D printing preparation method of a kind of bone defect repair support according to claim 5, is characterized in that, described hydrothermal temperature is 100-120 DEG C, and the response time is 40-50h.
8. the 3D printing preparation method of a kind of bone defect repair support according to claim 5, it is characterized in that, described silicon source is ethyl orthosilicate, and the mass ratio of described ethyl orthosilicate and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer is 2-3:1.
9. the 3D printing preparation method of a kind of bone defect repair support according to claim 5, is characterized in that, in described calcic mesoporous silicon material, calcium, silicon mol ratio are 0.5-2:1.
10. the 3D printing preparation method of a kind of bone defect repair support according to claim 1, it is characterized in that, the preparation method of described consolidation liquid is joined in polyvinyl alcohol water solution to be stirred to by sodium alginate to be uniformly dispersed, and obtains the poly-vinyl alcohol solution containing sodium alginate; Described is 1%-5% containing the mass fraction of sodium alginate in the poly-vinyl alcohol solution of sodium alginate.
CN201510836310.1A 2015-11-26 2015-11-26 3D printing preparation method of bond defect repair stent Pending CN105381505A (en)

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CN110669979A (en) * 2019-09-20 2020-01-10 江西理工大学 Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof
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CN107789081A (en) * 2016-08-31 2018-03-13 沈阳菲德莫尔科技有限公司 A kind of artificial tooth 3D mould printers
CN106730039A (en) * 2016-12-15 2017-05-31 中山职业技术学院 A kind of medical bone tissue reparation 3D printing material and preparation method thereof
CN106730039B (en) * 2016-12-15 2020-01-14 中山职业技术学院 3D printing material for medical bone tissue repair and preparation method thereof
CN108392673A (en) * 2018-02-26 2018-08-14 南昌大学 A kind of borosilicate bio-vitric/magnesium phosphate composite bone cement and its bone holder low temperature 3D printing method
CN108392673B (en) * 2018-02-26 2021-07-06 南昌大学 Borosilicate bioglass/magnesium phosphate composite bone cement and low-temperature 3D printing method of bone scaffold thereof
CN110075359A (en) * 2019-03-26 2019-08-02 华南理工大学 A kind of ultrasonic wave added prepares porous bone cement bracket and preparation method thereof
CN110075359B (en) * 2019-03-26 2021-09-21 华南理工大学 Ultrasonic-assisted preparation of porous bone cement scaffold and preparation method thereof
CN110669979A (en) * 2019-09-20 2020-01-10 江西理工大学 Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof
CN110669979B (en) * 2019-09-20 2021-11-26 江西理工大学 Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof
CN112245656A (en) * 2019-11-20 2021-01-22 武汉理工大学 Preparation method of calcium phosphate magnesium bone cement composite scaffold
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
CN112451744A (en) * 2020-11-11 2021-03-09 深圳大学 3D printing enzyme-containing bioactive scaffold, preparation method thereof and diabetic bone defect repair material

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