CN107160534A - A kind of 3 D-printing bioceramic compound rest and its application - Google Patents
A kind of 3 D-printing bioceramic compound rest and its application Download PDFInfo
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- CN107160534A CN107160534A CN201710347623.XA CN201710347623A CN107160534A CN 107160534 A CN107160534 A CN 107160534A CN 201710347623 A CN201710347623 A CN 201710347623A CN 107160534 A CN107160534 A CN 107160534A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/042—Iron or iron alloys
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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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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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
- A61L27/02—Inorganic materials
- A61L27/10—Ceramics or glasses
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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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention provides a kind of 3 D-printing bioceramic compound rest and its application, the compound rest is made by following methods：Biological ceramic powder, degradable metal powder, bio-vitric sintering aid powder and binder solution are mixed, slurry is obtained；Bio-vitric sintering aid powder is selected from silicate glass and/or phosphate glass；Slurry is printed using 3 D-printing method, compound rest base substrate is obtained；By the degreasing under oxygen-free environment of compound rest base substrate, then sinter, obtain bioceramic compound rest.The bioceramic compound rest is prepared by introducing degradable metal powder and particular kind of bio-vitric sintering aid powder in the feed by 3 D-printing method, makes its intensity height, good toughness, anti-fatigue performance good and pore structure controllable precise.The aperture of compound rest is 100~1000 μm, complete three-dimensional apertures connection, and porosity is 25~75%, and compression strength is 5~200MPa, and fracture toughness is 0.1~6MPam1/2。
Description
Technical field
The present invention relates to biology manufacture or biology medical material technical field, more particularly to a kind of 3 D-printing bioceramic
Compound rest and its application.
Background technology
Bioceramic is the preferred material of bone defect healing, mainly including calcium phosphate ceramic, silicate ceramics and calcium carbonate
Ceramics etc..Bioceramic is made after porous support, it is possible to achieve the osteoacusis in structure, promotes the degraded of material to be absorbed, from
And accelerate bone remoulding and regeneration.
Using conventional method (pore creating material method, freezing casting method, gas foaming method, Polymeric sponge method, etc.) prepare
Bioceramic scaffold is uneven due to pore structure, easily causes stress concentration, mechanical property can be caused drastically to decline.3 D-printing
Porous bioceramic scaffold pore structure uniform, controllable prepared by (also crying rapid shaping or increasing material manufacturing) method, complete three-dimensional apertures connect
Logical, its mechanical strength is substantially higher than support prepared by other method.However, there is big fragility, toughness all the time and resist in bioceramic
The poor inherent defect of fatigue behaviour, 3 D-printing bioceramic scaffold is restricted for non-weight bearing area or low weight bearing area bone
The reparation of defect.In addition, organic matter and liquid content are higher in the slurry that 3 D-printing is used, and the sintering character of bioceramic
It is poor, therefore in 3 D-printing bioceramic scaffold in addition to the macropore of design, the fiber played a supportive role also exists substantial amounts of
Micropore so that low intensity, the poor toughness of bioceramic scaffold.
The content of the invention
In view of this, should it is an object of the invention to provide a kind of 3 D-printing bioceramic compound rest and its application
Bioceramic compound rest intensity height and good toughness.
The invention provides a kind of bioceramic compound rest, it is made by following methods：
Biological ceramic powder, degradable metal powder, bio-vitric sintering aid powder and binder solution are mixed, obtained
Slurry；The bio-vitric sintering aid powder is selected from silicate glass and/or phosphate glass；
The slurry is printed using 3 D-printing method, compound rest base substrate is obtained；
By compound rest base substrate degreasing under oxygen-free environment, then sinter, obtain bioceramic compound rest.
Preferably, the bio-vitric sintering aid powder includes trace element；
The trace element is in magnesium elements, boron element, Zn-ef ficiency, ferro element, silver element, copper and strontium element
It is one or more.
Preferably, one or more of the degradable metal powder in iron, magnesium, ferroalloy and magnesium alloy.
Preferably, the biological ceramic powder is selected from calcium phosphate ceramic powder, silicate ceramics powder and calcium carbonate ceramics
One or more in powder.
Preferably, the calcium phosphate ceramic powder is selected from hydroxyapatite, bata-tricalcium phosphate, tetracalcium phosphate, alpha-phosphate three
One or more in calcium, calcium monohydrogen phosphate；
The silicate ceramics powder is selected from calcium silicates, dicalcium silicate, tricalcium silicate, akermanite, bredigite and silicon
One kind or more several in sour magnesium.
Preferably, the mass ratio of the biological ceramic powder, degradable metal powder and bio-vitric sintering aid powder is
35~99.8：0.1~64.9：0.1~64.9.
Preferably, the binding agent in the binder solution is selected from polyvinyl alcohol, methylcellulose, paraffin, polyethylene contracting
One or more in butyraldehyde, polyethylene glycol, synthetic rubber, polypyrrole alkanone and hydroxypropyl cellulose.
Preferably, the temperature of the sintering is 650~1300 DEG C；The time of the sintering is 1~300min.
Preferably, the aperture of the bioceramic compound rest is 100~1000 microns；The bioceramic compound rest
Porosity be 25~75%.
Prepared the invention provides bioceramic compound rest described in a kind of above-mentioned technical proposal in bone impairment renovation material
In application.
The invention provides a kind of bioceramic compound rest, it is made by following methods：By biological ceramic powder, degradable
Metal dust, bio-vitric sintering aid powder and binder solution mixing, obtain slurry；The bio-vitric sintering aid powder choosing
From silicate glass and/or phosphate glass；The slurry is printed using 3 D-printing method, compound rest base substrate is obtained；Will
Compound rest base substrate degreasing under oxygen-free environment, then sinters, obtains bioceramic compound rest.The life that the present invention is provided
Thing Ceramic Composite support is led to by introducing degradable metal powder and particular kind of bio-vitric sintering aid powder in the feed
The preparation of 3 D-printing method is crossed, makes its intensity height, good toughness.In addition, the compound rest anti-fatigue performance is good and pore structure accurately may be used
Control.Test result indicates that：The aperture of the bioceramic compound rest is 100~1000 μm, complete three-dimensional apertures connection, and porosity is
25~75%, compression strength is 5~200MPa, and fracture toughness is 0.1~6MPam1/2。
Embodiment
The invention provides a kind of bioceramic compound rest, it is made by following methods：
Biological ceramic powder, degradable metal powder, bio-vitric sintering aid powder and binder solution are mixed, obtained
Slurry；The bio-vitric sintering aid powder is selected from silicate glass and/or phosphate glass；
The slurry is printed using 3 D-printing method, compound rest base substrate is obtained；
By compound rest base substrate degreasing under oxygen-free environment, then sinter, obtain bioceramic compound rest.
The bioceramic compound rest that the present invention is provided by introducing degradable metal powder and particular types in the feed
Bio-vitric sintering aid powder, prepared by 3 D-printing method, make its intensity height, good toughness, anti-fatigue performance good and hole knot
Structure controllable precise.
In the present invention, the aperture of the bioceramic compound rest is preferably 100~1000 microns；The bioceramic
The porosity of compound rest is preferably 25~75%.Compression strength is preferably 5~200MPa, more preferably 5~150MPa.
The present invention mixes biological ceramic powder, degradable metal powder, bio-vitric sintering aid powder and binder solution
Close, obtain slurry；The bio-vitric sintering aid powder is selected from silicate glass and/or phosphate glass.In the present invention, institute
State biological ceramic powder be preferably selected from calcium phosphate ceramic powder, silicate ceramics powder and one kind in calcium carbonate ceramic powders or
It is a variety of；The calcium phosphate ceramic powder is preferably selected from hydroxyapatite, bata-tricalcium phosphate, tetracalcium phosphate, type alpha tricalcium phosphate, phosphoric acid
One or more in hydrogen calcium, are more preferably selected from the one or more in bata-tricalcium phosphate and hydroxyapatite；The silicate
Ceramic powders be preferably selected from one kind in calcium silicates, dicalcium silicate, tricalcium silicate, akermanite, bredigite and magnesium silicate or
It is more several, it is more preferably selected from the one or more in calcium silicates, akermanite and magnesium silicate.In the present invention, the biological pottery
The granularity of porcelain powder is preferably 0.1~200 μm.
In the present invention, the degradable metal powder is preferably selected from one kind or many in iron, magnesium, ferroalloy and magnesium alloy
Kind；In a particular embodiment of the present invention, the degradable metal powder is specially that pure iron powder, pure magnesium dust or ferrimanganic are closed
Gold.In the present invention, the granularity of the degradable metal powder is preferably 0.1~200 μm.In the present invention, it is described degradable
Metal dust can improve the intensity and toughness of compound rest.
In the present invention, the bio-vitric sintering aid powder is selected from silicate glass (SiO2- CaO systems) and/or phosphorus
Silicate glass (P2O5-Na2O systems)；Trace element is preferably included in the bio-vitric sintering aid powder；The trace element
Presence be beneficial to skeletonization and vascularization；The trace element is preferably selected from magnesium elements, boron element, Zn-ef ficiency, ferro element, silver dollar
One or more in element, copper and strontium element.In the present invention, the bio-vitric sintering aid powder can improve compound
The compactness of scaffold fibers support section.In the present invention, the granularity of the bio-vitric sintering aid powder be preferably 0.1~
200μm.In the present invention, the fusing point of the bio-vitric sintering aid powder is preferably 250~1250 DEG C.In the specific of the present invention
In embodiment, the bio-vitric sintering aid powder is specially the phosphate glass containing Zn and Cu, and its composition is 49P2O5-
23Na2O18CaO-5ZnO-5CuO；In one particular embodiment of the present invention, the bio-vitric sintering aid powder is specially
Phosphate glass containing Ag, its composition is 50P2O5-28Na2O-6AgO-16CaO；In one particular embodiment of the present invention,
The bio-vitric sintering aid powder is specially the phosphate glass containing Li and B, and its composition is 55P2O5-20Na2O-16CaO-
4Li2O-5B2O3；In one particular embodiment of the present invention, the bio-vitric sintering aid powder is specially the phosphoric acid containing Cu
Salt glass, its composition is 48P2O5-25Na2O-20CaO-7CuO；In one particular embodiment of the present invention, the biological glass
Glass sintering aid powder is specially the silicate glass containing B, and its composition is 45SiO2-30CaO-15Na2O-4P2O5-6B2O3；At this
Invention a specific embodiment in, the bio-vitric sintering aid powder be specially the silicate glass containing Zn and Sr, its into
It is divided into 50P2O5-25Na2O-10CaO-5ZnO-10SrO；In one particular embodiment of the present invention, the bio-vitric helps burning
Agent powder is specially the silicate glass containing B, and its composition is 49SiO2-39CaO-2P2O5-10B2O5-B2O3；The one of the present invention
In individual specific embodiment, the bio-vitric sintering aid powder is specially the silicate glass containing Sr, and its composition is 46P2O5-
23Na2O-15CaO-16SrO。
In the present invention, the quality of the biological ceramic powder, degradable metal powder and bio-vitric sintering aid powder
Than being preferably 35~99.8：0.1~64.9: 0.1~64.9.The present invention can be by controlling bioceramic composition, bio-vitric
Sintering aid composition is different with the degradation rate of degradable metal powdered ingredients, can be by changing component, the degraded of controlled material
Speed.In a particular embodiment of the present invention, the biological ceramic powder, degradable metal powder and bio-vitric sintering aid powder
The mass ratio at end is specially 60：25：15；Or 50: 20: 30；Or 45: 35: 20；Or 45: 20: 35；Or 80: 10: 10；Or 55：20∶
25；Or 65: 25: 10.
In the present invention, the binding agent in the binder solution be preferably selected from polyvinyl alcohol, methylcellulose, paraffin,
One or more in polyvinyl butyral, polyethylene glycol, synthetic rubber, polypyrrole alkanone and hydroxypropyl cellulose.It is described viscous
The mass concentration for tying agent solution is preferably 1~40%.The present invention does not have special limitation to the solvent in the binder solution,
Binding agent can be dissolved, solvent can be heated removing by end processing sequences.In the present invention, the quality of the binding agent with
The ratio of the biological ceramic powder, degradable metal powder and bio-vitric sintering aid powder gross mass is preferably 0.05~10：
100。
The present invention prints the slurry using 3 D-printing method, obtains compound rest base substrate.In the present invention, described three
It is three-dimensional drawing printing, inkjet printing, automatic grouting printing or fusion sediment printing to tie up the type of impact system.Specifically, this hair
The bright threedimensional model by compound rest base substrate is imported in three-dimensional printer, then the slurry is loaded to the material chamber of three-dimensional printer
In, fiber is extruded in the presence of compressed air, layer upon layer obtains compound rest base substrate.
Then compound rest base substrate degreasing under oxygen-free environment is sintered, obtains bioceramic composite support by the present invention
Frame.In the present invention, the oxygen-free environment preferably by nitrogen or argon gas or vacuumizes realization.In the present invention, the degreasing
The temperature of processing is preferably 200~750 DEG C；The time of the ungrease treatment is preferably 30~600min.In the present invention, it is described
Sintering is carried out preferably under nitrogen atmosphere or argon gas atmosphere；The temperature of the sintering is preferably 650~1300 DEG C；The sintering
Time is preferably 1~300min.
Present invention also offers bioceramic compound rest described in a kind of above-mentioned technical proposal in bone impairment renovation material system
Application in standby.
In the present invention, the bioceramic compound rest can be used for non-weight bearing area such as cancellous bone site, skull, jaw
The filling reparation of the Cranial defects such as face, can be used for partial weight-bearing position such as ulna, radius, upper mandibular, backbone, femur etc.
Bone defect healing.
The invention provides a kind of bioceramic compound rest, it is made by following methods：By biological ceramic powder, degradable
Metal dust, bio-vitric sintering aid powder and binder solution mixing, obtain slurry；The bio-vitric sintering aid powder choosing
From silicate glass and/or phosphate glass；The slurry is printed using 3 D-printing method, compound rest base substrate is obtained；Will
Compound rest base substrate degreasing under oxygen-free environment, then sinters, obtains bioceramic compound rest.The life that the present invention is provided
Thing Ceramic Composite support is led to by introducing degradable metal powder and particular kind of bio-vitric sintering aid powder in the feed
The preparation of 3 D-printing method is crossed, makes its intensity height, good toughness.In addition, the compound rest anti-fatigue performance is good and pore structure accurately may be used
Control.Test result indicates that：The aperture of the bioceramic compound rest is 100~1000 μm, complete three-dimensional apertures connection, and porosity is
25~75%, compression strength is 5~200MPa, and fracture toughness is 0.1~6MPam1/2。
In order to further illustrate the present invention, a kind of 3 D-printing bioceramic provided with reference to embodiment the present invention
Compound rest and its application are described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
The method of 3 D-printing bata-tricalcium phosphate Ceramic Composite support is：
By bata-tricalcium phosphate, (composition is 46P to the sintering aid of bio-vitric containing Sr2O5-23Na2) and pure iron O-15CaO-16SrO
Powder is added in methocel solution, and uniform mixture is obtained after ball milling.Bata-tricalcium phosphate, the sintering aid of bio-vitric containing Sr
Mass ratio with straight iron powder is 60：25∶15.The concentration of methocel solution is 1.5wt%.With bata-tricalcium phosphate, containing Sr lifes
The gross mass 100% of thing glass sintering aid, straight iron powder and carboxymethyl cellulose is counted, and the mass percent of carboxymethyl cellulose is
0.5%.
In the slurry chamber for filling this blend into automatic mortar injection forming machine, according to the three-dimensional mould of the scaffold three-dimensional structure of design
Type, printing obtains compound rest base substrate；Compound rest base substrate is put into stove, 650 DEG C of guarantors are to slowly warm up under vacuum
Warm 180min, is then placed in the sintering furnace of argon gas atmosphere, is warming up to 1100 DEG C, is incubated 120min, and Temperature fall obtains β-phosphorus
Sour DFP Ceramic Composite support, i.e. bioceramic compound rest.
The porosity that bata-tricalcium phosphate Ceramic Composite support is measured with μ-CT is 55%, and aperture is about 400 μm, uses omnipotent material
Material testing machine measures compression strength for 40MPa, and fracture toughness is 1.8MPam1/2。
Embodiment 2
The method of 3 D-printing calcium silicates Ceramic Composite support is：
By calcium silicates, the sintering aid of bio-vitric containing B (49SiO2-39CaO-2P2O5-10B2O5-B2O3) and the addition of pure magnesium powder
Uniform mixture is obtained in synthetic rubber solution, after ball milling.Calcium silicates, containing Si and B bio-vitrics sintering aid, the matter of pure magnesium powder
Amount is than being 50: 20: 30.The concentration of synthetic rubber is 9wt%.With calcium silicates, containing Si and B bio-vitrics sintering aid, pure magnesium powder and
The gross mass 100% of synthetic rubber is counted, and the mass percent of synthetic rubber is 6%.
In the slurry chamber for filling this blend into three-dimensional drawing machine, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 550 DEG C of insulations are to slowly warm up under vacuum
120min, is then placed in the sintering furnace of argon gas atmosphere, is warming up to 700 DEG C, is incubated 60min, and Temperature fall obtains calcium silicates pottery
Porcelain compound rest, i.e. bioceramic compound rest.
The porosity that calcium silicates Ceramic Composite support is measured with μ-CT is 45%, and aperture is about 600 μm, is tried with universal material
The machine of testing measures compression strength for 30MPa, and fracture toughness is 1.2MPam1/2。
Embodiment 3
The method of 3 D-printing calcium carbonate compound rest is：
By calcium carbonate, containing Zn and Sr bio-vitrics sintering aid, (composition is 50P2O5-25Na2O-10CaO-5ZnO-10SrO)
Added with pure magnesium powder in polyvinyl butyral solution, uniform mixture is obtained after ball milling.Calcium carbonate, containing the biological glass of Zn and Sr
Glass sintering aid, the mass ratio of pure magnesium powder are 45: 35: 20.Concentration in polyvinyl butyral solution is 7.5wt%.With carbonic acid
Calcium, the gross mass 100% containing Zn and Sr bio-vitrics sintering aid, pure magnesium powder and polyvinyl butyral resin are counted, polyvinyl alcohol contracting fourth
The mass percent of aldehyde is 1.5%.
In the slurry chamber for filling this blend into automatic grouting machine, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 550 DEG C of insulations are to slowly warm up under the conditions of argon gas
120min, is then warming up to 700 DEG C in argon gas atmosphere, is incubated 30min, and Temperature fall obtains calcium carbonate Ceramic Composite support, i.e.,
Bioceramic compound rest.
The porosity that calcium silicates composite ceramics support is measured with μ-CT is 40%, and aperture is about 350 μm, is tried with universal material
The machine of testing measures compression strength for 25MPa, and fracture toughness is 1MPam1/2。
Embodiment 4
The preparation method of bata-tricalcium phosphate/calcium silicates compound rest is as follows：
By bata-tricalcium phosphate, calcium silicates, the sintering aid of bio-vitric containing B (45SiO2-30CaO-15Na2O-4P2O5-6B2O3)、
Ferromanganese powder is added in paraffin solution, and uniform mixture is obtained after ball milling.Bata-tricalcium phosphate, calcium silicates, bio-vitric containing B
Sintering aid, the mass ratio of ferromanganese powder are 25: 35: 25: 15.The concentration of paraffin solution is 12wt%.With bata-tricalcium phosphate, silicon
Sour calcium, the sintering aid of bio-vitric containing B, the gross mass 100% of ferromanganese powder and paraffin are counted, and the mass percent of paraffin is 3%.
In the slurry chamber for filling this blend into fusion sediment type three-dimensional printer, according to the three of the scaffold three-dimensional structure of design
Dimension module, printing obtains compound rest base substrate；Compound rest base substrate is put into stove, 410 are to slowly warm up under a nitrogen atmosphere
DEG C, be incubated 120min, be then warming up to 1120 DEG C in nitrogen atmosphere, be incubated 120min, Temperature fall, obtain bata-tricalcium phosphate/
Calcium silicates composite ceramics support, i.e. bioceramic compound rest.
The porosity that bata-tricalcium phosphate/calcium silicates composite ceramics support is measured with μ-CT is 50%, and aperture is about 300 μm,
The compression strength that support is measured with universal testing machine is 90MPa, and fracture toughness is 2MPam1/2。
Embodiment 5
The preparation method of hydroxyapatite composite ceramics support is as follows：
By hydroxyapatite, (composition is 48P to the sintering aid of bio-vitric containing Cu2O5-25Na2O-20CaO-7CuO), iron powder adds
Enter in poly-vinyl alcohol solution, uniform mixture is obtained after ball milling.Hydroxyapatite, bio-vitric containing Cu sintering aid, iron powder
Mass ratio is 45：20：35.The concentration of poly-vinyl alcohol solution is 8wt%.With hydroxyapatite, the sintering aid of bio-vitric containing Cu, iron
The gross mass 100% of powder and polyvinyl alcohol is counted, and the mass percent of polyvinyl alcohol is 2%.
In the slurry chamber for filling this blend into three-dimensional drawing machine, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 600 DEG C of insulations are to slowly warm up under the conditions of argon gas
180min, is then warming up to 1250 DEG C in argon gas atmosphere, is incubated 120min, and Temperature fall obtains hydroxyapatite composite ceramics
Support, i.e. bioceramic compound rest.
The porosity that bata-tricalcium phosphate/hydroxyapatite composite ceramics support is measured with μ-CT is 40%, and aperture is about 200
μm, it is 150MPa that compression strength is measured with universal testing machine, and fracture toughness is 5MPam1/2。
Embodiment 6
The method of 3 D-printing akermanite composite ceramics support is as follows：
By akermanite, containing Li and B bio-vitrics sintering aid, (composition is 55P2O5-20Na2O-16CaO-4Li2O-5B2O3)
Added with iron powder in hydroxypropyl cellulose solution, uniform mixture is obtained after ball milling.Akermanite, containing Si and B bio-vitrics
Sintering aid, the mass ratio of iron powder are 80：10：10.The concentration of hydroxypropyl cellulose solution is 7wt%.With akermanite, containing Si and
The gross mass 100% of B bio-vitrics sintering aid, iron powder and hydroxypropyl cellulose is counted, and the mass percent of hydroxypropyl cellulose is
1.3%.
In the slurry chamber for filling this blend into automatic grouting machine, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 550 DEG C of insulations are to slowly warm up under vacuumized conditions
90min, is then warming up to 1150 DEG C in nitrogen atmosphere, is incubated 90min, and Temperature fall obtains akermanite composite ceramics support,
That is bioceramic compound rest.
The porosity that akermanite composite ceramics support is measured with μ-CT is 65%, and aperture is about 750 μm, uses universal material
Testing machine measures compression strength for 6MPa, and fracture toughness is 0.8MPam1/2。
Embodiment 7
The method of 3 D-printing magnesium silicate composite ceramics support is as follows：
By magnesium silicate, (composition is 50P to the sintering aid of bio-vitric containing Ag2O5-28Na2O-6AgO-16CaO), pure magnesium powder is added
Uniform mixture is obtained in poly-vinyl alcohol solution, after ball milling.Magnesium silicate, the sintering aid of bio-vitric containing Ag, the quality of pure magnesium powder
Than for 55：20：25.The concentration of polyvinyl alcohol is 8wt%.With magnesium silicic acid, the sintering aid of bio-vitric containing Ag, pure magnesium powder and polyethylene
The gross mass 100% of alcohol is counted, and the mass percent of polyvinyl alcohol is 1.4%.
In the slurry chamber for filling this blend into ink-jet printer, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 600 DEG C of insulations are to slowly warm up under an argon atmosphere
60min, is then warming up to 750 DEG C in nitrogen atmosphere, is incubated 60min, and Temperature fall obtains magnesium silicate composite ceramics support, i.e.,
Bioceramic compound rest.
The porosity that magnesium silicate composite ceramics support is measured with μ-CT is 43%, and aperture is about 460 μm, is tried with universal material
The machine of testing measures compression strength for 37MPa, and fracture toughness is 1.3MPam1/2。
Embodiment 8
The method of 3 D-printing type alpha tricalcium phosphate/hydroxyapatite composite ceramics support is as follows：
By type alpha tricalcium phosphate, hydroxyapatite, containing Zn and Cu bio-vitrics sintering aid, (composition is 49P2O5-
23Na2O18CaO-5ZnO-5CuO), ferromanganese powder is added in methocel solution, and uniform mixture is obtained after ball milling.
Type alpha tricalcium phosphate, hydroxyapatite, the mass ratio containing Zn and Cu bio-vitrics sintering aid, ferromanganese powder are 35: 30: 25: 10.
The concentration of methylcellulose is 0.9wt%.With type alpha tricalcium phosphate, hydroxyapatite, containing Zn and Cu bio-vitrics sintering aid, ferrimanganic
The gross mass 100% of alloyed powder and methylcellulose is counted, and the mass percent of methylcellulose is 0.3%.
In the slurry chamber for filling this blend into automatic grouting machine, according to the threedimensional model of the scaffold three-dimensional structure of design, beat
Print obtains compound rest base substrate；Compound rest base substrate is put into stove, 540 DEG C of insulations are to slowly warm up under an argon atmosphere
120min, is then warming up to 1200 DEG C under vacuumized conditions, is incubated 120min, and Temperature fall obtains type alpha tricalcium phosphate/hydroxyl
Apatite composite ceramics support, i.e. bioceramic compound rest.
The porosity that type alpha tricalcium phosphate/hydroxyapatite composite ceramics support is measured with μ-CT is 58%, and aperture is about 550
μm, it is 60MPa that compression strength is measured with universal testing machine, and fracture toughness is 3MPam1/2。
As seen from the above embodiment, the invention provides a kind of bioceramic compound rest, it is made by following methods：Will be raw
Thing ceramic powders, degradable metal powder, bio-vitric sintering aid powder and binder solution mixing, obtain slurry；The life
Thing glass sintering aid powder is selected from silicate glass and/or phosphate glass；The slurry is printed using 3 D-printing method, obtained
To compound rest base substrate；By compound rest base substrate degreasing under oxygen-free environment, then sinter, obtain bioceramic composite support
Frame.The bioceramic compound rest that the present invention is provided by introducing degradable metal powder and particular kind of biology in the feed
Glass sintering aid powder, is prepared by 3 D-printing method, makes its intensity height, good toughness.In addition, the compound rest anti-fatigue performance
Good and pore structure controllable precise.Test result indicates that：The aperture of the bioceramic compound rest is 100~1000 μm, complete three
Hole connection is tieed up, porosity is 25~75%, compression strength is 5~200MPa, fracture toughness is 0.1~6MPam1/2。
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of bioceramic compound rest, is made by following methods：
Biological ceramic powder, degradable metal powder, bio-vitric sintering aid powder and binder solution are mixed, starched
Material；The bio-vitric sintering aid powder is selected from silicate glass and/or phosphate glass；
The slurry is printed using 3 D-printing method, compound rest base substrate is obtained；
By compound rest base substrate degreasing under oxygen-free environment, then sinter, obtain bioceramic compound rest.
2. bioceramic compound rest according to claim 1, it is characterised in that in the bio-vitric sintering aid powder
Including trace element；
The one kind of the trace element in magnesium elements, boron element, Zn-ef ficiency, ferro element, silver element, copper and strontium element
Or it is a variety of.
3. bioceramic compound rest according to claim 1, it is characterised in that the degradable metal powder is selected from
One or more in iron, magnesium, ferroalloy and magnesium alloy.
4. bioceramic compound rest according to claim 1, it is characterised in that the biological ceramic powder is selected from phosphoric acid
One or more in calcium ceramic powders, silicate ceramics powder and calcium carbonate ceramic powders.
5. bioceramic compound rest according to claim 4, it is characterised in that the calcium phosphate ceramic powder is selected from hydroxyl
One or more in base apatite, bata-tricalcium phosphate, tetracalcium phosphate, type alpha tricalcium phosphate, calcium monohydrogen phosphate；
The silicate ceramics powder is selected from calcium silicates, dicalcium silicate, tricalcium silicate, akermanite, bredigite and magnesium silicate
In one kind or more several.
6. bioceramic compound rest according to claim 4, it is characterised in that the biological ceramic powder, degradable
The mass ratio of metal dust and bio-vitric sintering aid powder is 35~99.8：0.1~64.9：0.1~64.9.
7. bioceramic compound rest according to claim 1, it is characterised in that the binding agent in the binder solution
Selected from polyvinyl alcohol, methylcellulose, paraffin, polyvinyl butyral, polyethylene glycol, synthetic rubber, polypyrrole alkanone and hydroxypropyl
One or more in base cellulose.
8. bioceramic compound rest according to claim 1, it is characterised in that the temperature of the sintering is 650~
1300℃；The time of the sintering is 1~300min.
9. bioceramic compound rest according to claim 1, it is characterised in that the hole of the bioceramic compound rest
Footpath is 100~1000 microns；The porosity of the bioceramic compound rest is 25~75%.
10. a kind of the answering in bone impairment renovation material preparation of bioceramic compound rest described in claim 1~9 any one
With.
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