CN108187149A - A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method - Google Patents
A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method Download PDFInfo
- Publication number
- CN108187149A CN108187149A CN201810121496.6A CN201810121496A CN108187149A CN 108187149 A CN108187149 A CN 108187149A CN 201810121496 A CN201810121496 A CN 201810121496A CN 108187149 A CN108187149 A CN 108187149A
- Authority
- CN
- China
- Prior art keywords
- printing
- degradation
- bone tissue
- tissue engineering
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Transplantation (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of controllable bone tissue engineering scaffolds of the degradation based on 3D printing and preparation method thereof, solves the problem of careful design manufacture that bone impairment renovation material in the prior art can not ensure microcellular structure, Effective Regulation can not be carried out to the degradation speed of material.Stent of the present invention is porous structure, and porosity is 60%~95%, and hole wall backing material string diameter is 100 μm~800 μm, is successively printed by a kind of ink raw material or is printed by least two different ink raw material layerings.The method of the present invention is to prepare the ink raw material of 3D printing；Model is established, hierarchy slicing processing then is carried out to institute's established model, designed threedimensional model is inputted in three-dimensional jet printer, carries out printing precise forming target idiosome layer by layer, and the idiosome is calcined to get degradation controllable biological ceramics.The controllable bone tissue engineering scaffold of degradation of the present invention can guarantee the careful design molding of microcellular structure, it can be achieved that combination assembling of the material on three dimensions of different degradation speeds, realize the Effective Regulation to material degradation speed.
Description
Technical field
The invention belongs to technical field of biomedical materials, and in particular to a kind of controllable bone of biological degradation based on 3D printing
Tissue engineering bracket and preparation method.
Background technology
Bone impairment renovation material is always one of research hotspot of technical field of biological material.Osseous tissue renovating material is as a kind of
Special biomaterial has particular/special requirement functionally：Load mechanical property, biocompatibility, osteoconductive and self-bone grafting
Property.In recent years since degradable artificial bone tissue engineer repair materials have many advantages, such as, it is made to be increasingly becoming bone renovating material
The direction of development.Bioactivity calcium phosphate ceramics contain CaO and P2O5Two kinds of ingredients, they are the important of composition body bone tissue
Inorganic substances, after being implanted into human body, surface can reach bio-compatible with tissue by the combination of chemical bond, be ideal bone
Repair materials.Calcium phosphate ceramic material mainly includes hydroxyapatite (HA) and tricalcium phosphate (TCP).Hydroxyapatite
The chemical formula of (hydroxyapatite, HA) is Ca10(PO4)6(OH)2, be space group be P63The crystallization knot of the hexagonal crystal system of/m
Structure, lattice parameter a=b=0.942/nm, c=0.6875nm, Ca/P element ratios are 1.67.HA in the Nomenclature Composition and Structure of Complexes and people's bone and
The inanimate matter of tooth is quite similar, but solution rate in vivo is slower.The ingredient of TCP is compared with HA, and Ca, P element ratio are not
Together, wherein β-TCP are most widely used.β-TCP belong to trigonal system, lattice constantTheoretical density is
3.07g/cm3.Space group is R3C, calcium phosphorus atoms ratio is 1.5, is a kind of high-temperature-phase of calcium phosphate.β-TCP are in aqueous solution and body fluid
In solubility be 10~15 times of HA, can slowly be degraded and absorbed.During this, calcium phosphate ceramic is degraded to new bone formation
More rich Ca, P are provided, promote new bone tissue generation, and gradually replace new bone tissue.The drop of calcium phosphate ceramic stent in vivo
Solution rate and the growth rate of new bone, which match, just can guarantee the normal growth of stent mechanical property in vivo and new bone, still
Currently for such issues that there are no a kind of good solution, this is also that bone graft biomaterial substitutes clinical practice needs will solve
A great problem certainly.
The effect of Calcium phosphate biomaterials induced osteogenesis is influenced by its composition and structure, usual TCP/HA two-phases porous ceramics
It is easy to induced osteogenesis than HA porous ceramics.The porosity of physical characteristic such as material, aperture, distribution of pores and its whether penetrate through, with
And mechanical performance etc., its osteoinductive is influenced also very big.(YuanHP, et, al.J the Mater Sci, Mater such as Yuan
Med,2001；12 (1): the calcium phosphate ceramic of different materials composition 7) is selected to carry out zoopery, it is believed that have what is be mutually communicated
Macropore, and have on macropore the ceramic osteoinductive of micropore of abundant a few micrometers to some tens of pm good.It therefore, can Precise spraying
The microcellular structure of manufacture plays the osteoinductive of calcium phosphate ceramic crucial regulating and controlling effect, although there is many techniques can be at present
Porous calcium phosphate ceramic is produced, but traditional process can not ensure the careful design manufacture of microcellular structure, it can not be right
Different materials are combined assembling, can not realize the Effective Regulation of degradation speed.
Therefore it provides a kind of degradable bone tissue engineering scaffold, can guarantee the careful design manufacture of microcellular structure, realizes
The combination assembling of different degradation property materials, so as to fulfill the Effective Regulation to implant degradation speed, becomes this field skill
Art personnel's urgent problem to be solved.
Invention content
Present invention solves the technical problem that it is：A kind of controllable bone tissue engineering scaffold of the degradation based on 3D printing is provided, is solved
Certainly bone impairment renovation material can not ensure the careful design manufacture of microcellular structure in the prior art, it is impossible to carry out group to different materials
The problem of attaching together and match, can not realizing the Effective Regulation to implant degradation speed.
The present invention also provides the preparation methods of the controllable bone tissue engineering scaffold of the degradation based on 3D printing.
The technical solution adopted by the present invention is as follows：
The controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing of the present invention, the stent are porous knot
Structure, porosity are 60%~95%, and hole wall backing material string diameter is 100 μm~800 μm, and the stent is by same ink printed
It forms or is printed by the ink of at least two different degradation rates through different printing heads.
Further, the stent has the macropore to interpenetrate, and capillary micropore is enriched on the macropore inner wall.
Further, the aperture of the macropore is 50 μm~1600 μm, and the aperture of the capillary micropore is the μ of 500nm~10
m。
Further, when the stent is formed for the ink printed of same raw material configuration, the gross mass of raw material is pressed
100% meter, including following components：Biphasic calcium phosphate 40~60wt.% of powder, 20~50wt.% of water, 5~10wt.% of ethyl alcohol,
3~5wt.% of polyvinyl alcohol, 2~5wt.% of amylalcohol；
When the stent is printed for the ink of two kinds of different degradation rates through different printing heads, the original of each ink
Gross mass is expected based on 100%, including 40~60wt.% of single calcium powder material, 50~20wt.% of water, 5~10wt.% of ethyl alcohol, is gathered
3~5wt.% of vinyl alcohol, 2~5wt.% of amylalcohol；The single calcium powder material is any one in hydroxyapatite, tricalcium phosphate
Kind.
Further, the quality of the biphasic calcium phosphate powder is based on 100%, the hydroxyapatite including 10~90wt%
With the tricalcium phosphate of 10~90wt%.
Further, the diameter of particle of the hydroxyapatite and tricalcium phosphate is 50nm~100 μm.
A kind of preparation method of controllable bone tissue engineering scaffold of degradation based on 3D printing of the present invention, specifically includes
Following steps：
Step 1：Prepare the ink of 3D printing：The each component of ink raw material is weighed in proportion, is configured to same ink and is contained
Different raw material mass mixture ratios or several different inks；
Step 2：3D printing：It first passes through and model is established in modeling software, institute's established model is carried out then in conjunction with delamination software
Hierarchy slicing processing, and internal printed material string diameter, the spacing of adjacent spinneret and the spinneret of adjacent layer supported is set to intersect
Angle, designed threedimensional model is inputted in three-dimensional jet printer, and marking ink raw material is added to 3 D-printing
In machine, the printing precise forming target idiosome that is layering is carried out；
Step 3：By the idiosome calcine to get.
Further, in step 1, when preparing several different inks, each ink corresponds to a printing head, passes through
Different printing head printings realizes that different material interleaves printing assembling or ladder in the 3d space material above of the stent
Degree design printing.
Further, the print speed is 2~6mm/s.
Further, in step 3, the idiosome is put into Muffle furnace and is calcined, 600 are warming up to the rate of 5 DEG C/min
DEG C, 2 hours are kept the temperature at 600 DEG C, then 1100 DEG C is warming up to 5 DEG C/min and keeps the temperature 2 hours at 1100 DEG C, finally with furnace cooling
But.
Compared with prior art, the invention has the advantages that：
Present invention process is simple, easy to operate, can guarantee the careful design manufacture of microcellular structure, realizes to material degradation speed
The Effective Regulation of degree.
Present invention process is simple, easy to operate, the raw material with different degradation rates can be realized three by 3D printing
Arbitrary combination assembling on dimension space, realizes the Effective Regulation to implant degradation speed.The present invention passes through different degradations are fast
Spending the raw material mixed configuration of characteristic becomes marking ink, by controlling starting components ratio that can realize the degradation of final products
Speed control；Hole is printed by control, the diameter of each spinneret line particularly printed is, it can be achieved that implant
The control of degradation speed；By double nozzles or more nozzles, it can realize different component raw material on stent 3d space
Material assembles or gradient design printing, realizes the degradation speed control of stent different parts.
The bone tissue engineering stent material of the present invention has interconnected macropore and small capillary microcellular structure, macropore
Be conducive to tissue grow into and angiogenic growth, micropore are conducive to that nutriment interaction, body fluid circulation, osteoblast is in material surface
Adherency, growth and differentiation.
Present invention uses 3 D-printing (3D) rapid shaping technique, no extra waste cut materials generate, and stock utilization is big
Subtract manufacture process better than tradition greatly, there is good economic benefit.
The present invention engineering rack preparation process in, it is no chemical reaction and organic solvent participate in, avoid it is toxic,
Pollution of the harmful substance to biomaterial.
The engineering rack of the present invention has good structural intergrity and shape customization capability, can be lacked according to patient's bone tissue
Reparation demand is damaged, is processed into variously-shaped, meets patient personalized medical demand.
Description of the drawings
Fig. 1 is ink to be configured using different raw materials in embodiment 1 degradation behavior of bone tissue engineering scaffold is controlled to illustrate
Figure.
Fig. 2 is the degradation behavior schematic diagram using different pore structure design control stents.
Fig. 3 is using different ink raw materials, and print control scaffold degradation behavior schematic diagram is interleave through different nozzles.
Micro- pore structure SEM figures of the Fig. 4 for controllable bone tissue engineering scaffold of degrading in the embodiment of the present invention 1, wherein (a) is
Macropore SEM schemes, and (b) schemes for capillary micropore SEM.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment, to the present invention
It is further elaborated.It should be appreciated that specific embodiment herein is not used to limit this hair only to explain the present invention
It is bright.The present invention degrades controllable bone tissue engineering scaffold for repairing the defect of human body hard bone tissue, and degradation of the invention is controllable
Pore structure design and material component proportioning are not limited to scheme of the present invention used by bone tissue engineering scaffold.
Embodiment 1-7 is the degradation behavior using different raw material configuration ink control stents：
Embodiment 1
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
Taking hydroxyapatite (HA), tricalcium phosphate powder (β-TCP) is as raw material 2, by raw material 1 and raw material 2 as raw material 1
In mass ratio 60:40 ratio is uniformly mixed, and obtains mixed powder.Polyvinyl alcohol 10g is taken, water 90ml is added to dissolve, is configured to gather
Glycohol solution.20ml poly-vinyl alcohol solutions are uniformly blended into the mixed powder of 32.5g, add in 7ml's while stirring
Deionized water and 6ml absolute ethyl alcohols until stirring evenly, obtain marking ink raw material.Wherein, hydroxyapatite and tricalcium phosphate
Diameter of particle be 50nm~100 μm.
In modeling software, 10mm × 10mm × 3mm cubes are established, institute's established model is carried out then in conjunction with delamination software
Hierarchy slicing processing, it is 400 μm to set the internal printed material string diameter supported, and the spacing of adjacent spinneret is 800 μm, adjacent layer
The angle that spinneret intersects is 90 °.The threedimensional model of design is converted into STL forms, is inputted in three-dimensional jet printer, setting is beaten
Print-out rate is 2mm/s, and marking ink raw material is added in three-dimensional printer, carries out the printing precise forming target that is layering
Idiosome.
Finally idiosome is put into Muffle furnace and is calcined, 600 DEG C are warming up to the rate of 5 DEG C/min, it is small in 600 DEG C of heat preservations 2
When, then 1100 DEG C being warming up to 5 DEG C/min and keeping the temperature 2 hours at 1100 DEG C, last furnace cooling, obtaining porosity is
74.4%, aperture is 400 ± 20 μm of biophasic calcium phosphate ceramic bone tissue engineering scaffold, and the degradation speed of stent is higher than pure hydroxyl
The stent of apatite (HA) raw material printing, but is below the stent printed by pure phosphoric acid tricalcium (β-TCP), this is because mixing is former
After material 1 and 2, marking ink degradation speed embodies a kind of compromise effect.
Embodiment 2
Present embodiments provide the preparation for controllable bone tissue engineering scaffold of degrading.The modeling and sintering of stent in the present embodiment
For process with embodiment 1, the difference lies in carry out matching for 3D printing ink raw material using the batching mode different from embodiment 1
It puts, specially：
Polyvinyl alcohol 10g is taken, water 90ml is added to dissolve, is configured to poly-vinyl alcohol solution.20ml poly-vinyl alcohol solutions is uniform
It adds in the hydroxyapatite (HA) of 32.5g, the deionized water of 7ml and 6ml absolute ethyl alcohols is added in while stirring, until stirring
It mixes uniformly, obtains marking ink raw material.Wherein, hydroxy apatite powder grain size is 50nm~100 μm.
Then it with the model 3D printing of embodiment 1 and sinters porcelain into, obtains HA ceramics bone tissue engineering scaffolds.The present embodiment
The degradation speed of middle stent is less than the degradation speed in embodiment 1, this is because the degradation speed of this raw material HA is less than embodiment 1
In mixing material.
Embodiment 3
Present embodiments provide the preparation for controllable bone tissue engineering scaffold of degrading.The modeling and sintering of stent in the present embodiment
For process with embodiment 1, the difference lies in carry out matching for 3D printing ink raw material using the batching mode different from embodiment 1
It puts, specially：
Polyvinyl alcohol 10g is taken, water 90ml is added to dissolve, is configured to poly-vinyl alcohol solution.20ml poly-vinyl alcohol solutions is uniform
It adds in the tricalcium phosphate (β-TCP) of 32.5g, the deionized water of 7ml and 6ml absolute ethyl alcohols is added in while stirring, until
It stirs evenly, obtains marking ink raw material.The diameter of particle of wherein tricalcium phosphate is 50nm~100 μm.
Then it with the model 3D printing of embodiment 1 and sinters porcelain into, obtains β-TCP ceramics bone tissue engineering scaffolds.This reality
The degradation speed of stent in example is applied higher than the degradation speed in embodiment 1, this is because the degradation speed of this raw material β-TCP is higher than
Mixing material in embodiment 1.
Embodiment 4
Present embodiments provide the preparation for controllable bone tissue engineering scaffold of degrading, compared with Example 1, hydroxyl in the present embodiment
The mass ratio of base apatite and tricalcium phosphate is 50:50, remaining condition all same, it is 74.4% to finally obtain porosity, aperture
For 400 ± 20 μm of biophasic calcium phosphate ceramic bone tissue engineering scaffold.
The internal degradation rate of stent is 4 ＞ embodiments 1 of embodiment.The reason is that degradation rate in stenter to implant body by
The influence of marking ink material component improves the β-TCP in marking ink material with higher degradation rate, can control raising
The degradation rate of final print carriage material.
Embodiment 5
Present embodiments provide the preparation for controllable bone tissue engineering scaffold of degrading, compared with Example 1, hydroxyl in the present embodiment
The mass ratio of base apatite (HA) and tricalcium phosphate (β-TCP) is 40:60, remaining condition all same, finally obtaining porosity is
74.4%, aperture is 400 ± 20 μm of biophasic calcium phosphate ceramic bone tissue engineering scaffold.
The internal degradation rate of stent is 5 ＞ embodiments 4 of embodiment.The reason is that degradation rate in stenter to implant body by
The influence of marking ink material component improves the β-TCP in marking ink material with higher degradation rate, can control raising
The degradation rate of final print carriage material.
Embodiment 6
Compared with Example 1, the configuration of marking ink is different, remaining condition all same for the present embodiment.
Tricalcium phosphate powder (β-TCP), will be former as raw material 2 as raw material 1 for the hydroxyapatite (HA) that takes of marking ink
Material 1 and raw material 2 in mass ratio 60:40 ratio is uniformly mixed, and obtains mixed powder.Wherein, hydroxyapatite and tricalcium phosphate
Diameter of particle be 50nm~100 μm.
Marking ink raw material gross mass is based on 100%, mixed powder 60wt.%, water 20wt.%, ethyl alcohol 10wt.%,
Polyvinyl alcohol 5wt.%, amylalcohol 5wt.%；Said components are uniformly mixed to get marking ink.
The degradation speed no significant difference of the degradation speed of stent and stent in embodiment 1 in the present embodiment.
Embodiment 7
Compared with Example 1, the configuration of marking ink is different, remaining condition all same for the present embodiment.
Tricalcium phosphate powder (β-TCP), will be former as raw material 2 as raw material 1 for the hydroxyapatite (HA) that takes of marking ink
Material 1 and raw material 2 in mass ratio 60:40 ratio is uniformly mixed, and obtains mixed powder.Wherein, hydroxyapatite and tricalcium phosphate
Diameter of particle be 50nm~100 μm.
Marking ink raw material gross mass is based on 100%, mixed powder 40wt.%, water 50wt.%, ethyl alcohol 5wt.%, gathers
Vinyl alcohol 5wt.%；Said components are uniformly mixed to get marking ink.
The degradation speed no significant difference of the degradation speed of stent and stent in embodiment 1 in the present embodiment.
Embodiment 8-10 is the embodiment using the degradation behavior of different pore structure design control stents：
Embodiment 8
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
The configuration of 3D printing ink raw material is carried out with batching mode in embodiment 1.
In modeling software, 10mm × 10mm × 3mm cubes are established, institute's established model is carried out then in conjunction with delamination software
Layered shaping, it is 300 μm to set the internal filament diameter supported, and the distance of adjacent two silks is 800 μm, the filament phase of adjacent layer
The angle of friendship is 90 °.
Remaining subsequent step is with embodiment 1, and it is 80% to finally obtain porosity, and aperture is 500 ± 20 μm of two-phase phosphorus
Sour calcium ceramics bone tissue engineering scaffold.
The internal degradation rate of the present embodiment stent will be above the biphasic calcium phosphate bone tissue engineering scaffold in embodiment 1,
Because the internal microcellular structure with small diameter is supported with faster degradation rate.
Embodiment 9
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
The configuration of 3D printing ink raw material is carried out with batching mode in embodiment 1.
In modeling software, 10mm × 10mm × 3mm cubes are established, institute's established model is carried out then in conjunction with delamination software
Layered shaping, it is 300 μm to set the internal filament diameter supported, and the distance of adjacent two silks is 1000 μm, the filament of adjacent layer
Intersecting angle is 90 °.
Remaining subsequent step is with embodiment 1, and it is 82% to obtain porosity, and aperture is 700 ± 20 μm of biphasic calcium phosphate
Ceramic bone tissue engineering scaffold.
The internal degradation rate of stent is 7 ＞ embodiments of embodiment, 6 ＞ embodiments 1.Controllable principle of wherein degrading such as Fig. 2 institutes
Show, since the degradation rate in stenter to implant body is influenced by material microcellular structure, the diameter of backing material is thinner, pitch of holes more
Greatly, degradation speed is faster, otherwise carries out pore structure design printing and then its degradation speed can control to slow down.
Embodiment 10
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
The configuration of 3D printing ink raw material is carried out with batching mode in embodiment 1.
In modeling software, 10mm × 10mm × 3mm cubes are established, institute's established model is carried out then in conjunction with delamination software
Layered shaping, it is 250 μm to set the internal filament diameter supported, and the distance of adjacent two silks is 800 μm, the filament phase of adjacent layer
The angle of friendship is 90 °.Setting print speed is 5mm/s, remaining subsequent step is with embodiment 1, and it is 85% to obtain porosity, hole
Diameter is 500 ± 20 μm of biophasic calcium phosphate ceramic bone tissue engineering scaffold.
The internal degradation rate of stent is 8 ＞ embodiments of embodiment, 7 ＞ embodiments, 6 ＞ embodiments 1.Wherein degradation is controllable former
Reason as shown in Fig. 2, since the degradation rate in stenter to implant body is influenced by material microcellular structure, get over by the diameter of backing material
Carefully, pitch of holes is bigger, and degradation speed is faster, otherwise carries out pore structure design printing and then its degradation speed can control to slow down.
Embodiment 11-13 is using different ink raw materials, and print control scaffold degradation behavior is interleave through different nozzles
Embodiment：
Embodiment 11
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, software modeling and ceramic post sintering process are such as
With embodiment 1, the difference lies in using double ink materials of the nozzle gradient printing with different degradation rates.Specially：
Polyvinyl alcohol 10g is taken, water 90ml is added to dissolve, is configured to poly-vinyl alcohol solution.
The preparation of marking ink 1：Hydroxyapatite (HA) 32.5g is taken, adds in 20ml poly-vinyl alcohol solutions, on one side stirring one
Side adds in the deionized water of 7ml and 6ml absolute ethyl alcohols, until stirring evenly, obtains marking ink 1.
The preparation of marking ink 2：Tricalcium phosphate powder (β-TCP) 32.5g is taken, adds in 20ml poly-vinyl alcohol solutions, on one side
Stirring adds in the deionized water of 7ml and 6ml absolute ethyl alcohols on one side, until stirring evenly, obtains marking ink 2.
It is controlled in the present embodiment using marking ink 1 by nozzle 1, marking ink 2 is controlled by nozzle 2, and print carriage is such as
The top degradation speed of gradient degradation rate stent shown in Fig. 3, wherein stent is more than frame bottom, this is because frame upper
Employ the faster β-TCP ink printeds of degradation rate.
Embodiment 12
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
The configuration of 3D printing ink raw material is carried out with batching mode in embodiment 11, obtains 2 kinds of different marking inks, it is soft
Part models and ceramic post sintering process is such as embodiment 1, and the difference lies in different using double nozzle gradient print structure settings.
In the present embodiment, marking ink 1 is controlled by nozzle 1, and marking ink 2 is controlled by nozzle 2.Stent middle layer separating material
When expecting printing alternate, control 2 rows of printing of nozzle 1 are inserted with the printing of nozzle 2 and interleave 1 row, i.e. nozzle 1：Nozzle 2 prints number and accounts for
Than being 2：1, print carriage finally embodies intermediate double nozzles and interleaves printable layer with the degradation speed more slightly lower than in embodiment 9,
10 ＜ embodiments 9 of embodiment, this is because the HA materials accounting with relatively slow degradation rate in this layer is higher than embodiment 9.
Embodiment 13
The preparation for controllable bone tissue engineering scaffold of degrading is present embodiments provided, specially：
The configuration of 3D printing ink raw material is carried out with batching mode in embodiment 11, obtains 2 kinds of different marking inks, it is soft
Part models and ceramic post sintering process is such as embodiment 1, different the difference lies in being set using double nozzle gradient print structures,
Software modeling and ceramic post sintering process are such as embodiment 1.
In the present embodiment, marking ink 1 is controlled by nozzle 1, and marking ink 2 is controlled by nozzle 2.Stent middle layer separating material
When expecting printing alternate, control 1 row of printing of nozzle 1 is inserted with the printing of nozzle 2 and interleaves 2 rows, i.e. nozzle 1：Nozzle 2 prints number and accounts for
Than being 1：2, print carriage finally embodies intermediate double nozzles and interleaves printable layer with the degradation speed more slightly higher than in embodiment 9,
Degradation speed is 11 ＞ embodiments of embodiment, 9 ＞ embodiments 10, this is because the HA materials with relatively slow degradation rate in this layer
Expect that accounting is less than embodiment 9.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit the protection model of the present invention
Enclose, as long as the present invention body design thought and that mentally makes have no the change of essential meaning or polishing, solved
The technical issues of it is still consistent with the present invention, should all be included within protection scope of the present invention.
Claims (10)
1. a kind of controllable bone tissue engineering scaffold of degradation based on 3D printing, which is characterized in that the stent be porous structure, hole
Gap rate is 60%~95%, and hole wall backing material string diameter is 100 μm~800 μm, and the stent is formed by same ink printed,
Either printed by the ink of at least two different degradation rates through different printing heads.
A kind of 2. controllable bone tissue engineering scaffold of degradation based on 3D printing according to claim 1, which is characterized in that institute
Stating stent has the macropore to interpenetrate, and capillary micropore is enriched on the macropore inner wall.
A kind of 3. controllable bone tissue engineering scaffold of degradation based on 3D printing according to claim 2, which is characterized in that institute
The aperture for stating macropore is 50 μm~1600 μm, and the aperture of the capillary micropore is 500nm~10 μm.
4. the controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing according to claim 1-3 any one,
It is characterized in that, when the stent is formed by same ink printed, the gross mass of the raw material of the same ink presses 100%
Meter, including following components：Biphasic calcium phosphate 40~60wt.% of powder, 20~50wt.% of water, 5~10wt.% of ethyl alcohol, polyethylene
3~5wt.% of alcohol, 2~5wt.% of amylalcohol；
When the stent is printed for the ink of two kinds of different degradation rates through different printing heads, the raw material of each ink is total
Quality is based on 100%, including 40~60wt.% of single calcium powder material, 50~20wt.% of water, 5~10wt.% of ethyl alcohol, polyethylene
3~5wt.% of alcohol, 2~5wt.% of amylalcohol；Any one of the single calcium powder material in hydroxyapatite, tricalcium phosphate.
A kind of 5. controllable bone tissue engineering scaffold of degradation based on 3D printing according to claim 4, which is characterized in that institute
The quality of biphasic calcium phosphate powder is stated based on 100%, the phosphoric acid of hydroxyapatite and 10~90wt% including 10~90wt%
Tricalcium.
A kind of 6. controllable bone tissue engineering scaffold of degradation based on 3D printing according to claim 5, which is characterized in that institute
The diameter of particle for stating hydroxyapatite and tricalcium phosphate is 50nm~100 μm.
7. a kind of system of controllable bone tissue engineering scaffold of degradation based on 3D printing according to claim 1-6 any one
Preparation Method, which is characterized in that specifically include following steps：
Step 1：Prepare the ink of 3D printing：The each component of ink raw material is weighed in proportion, is configured to same ink containing difference
Raw material mass mixture ratio or several different inks；
Step 2：3D printing：It first passes through and model is established in modeling software, institute's established model is layered then in conjunction with delamination software
Slicing treatment, and the angle that internal printed material string diameter, the spacing of adjacent spinneret and the spinneret of adjacent layer supported is set to intersect
Designed threedimensional model is inputted in three-dimensional jet printer, and marking ink raw material is added in three-dimensional printer by degree,
Carry out the printing precise forming target idiosome that is layering；
Step 3：By the idiosome calcine to get.
8. preparation method according to claim 7, which is characterized in that in step 1, when preparing several different inks, often
A kind of ink corresponds to a printing head, is printed by different printing heads, realizes that different material is empty in the 3D of the stent
Between material above interleave printing assembling or gradient design printing.
9. preparation method according to claim 7, which is characterized in that the print speed is 2~6mm/s.
10. preparation method according to claim 7, which is characterized in that in step 3, the idiosome is put into Muffle furnace
Calcining, 600 DEG C are warming up to the rate of 5 DEG C/min, are kept the temperature 2 hours at 600 DEG C, are then warming up to 1100 DEG C simultaneously with 5 DEG C/min
2 hours are kept the temperature at 1100 DEG C, last furnace cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810121496.6A CN108187149A (en) | 2018-02-07 | 2018-02-07 | A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810121496.6A CN108187149A (en) | 2018-02-07 | 2018-02-07 | A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108187149A true CN108187149A (en) | 2018-06-22 |
Family
ID=62593128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810121496.6A Pending CN108187149A (en) | 2018-02-07 | 2018-02-07 | A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108187149A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技（固安）有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
| CN109172044A (en) * | 2018-07-24 | 2019-01-11 | 西安交通大学 | A kind of degradable gradient-porosity mammary gland bracket |
| CN109650872A (en) * | 2019-02-20 | 2019-04-19 | 四川大学 | A kind of calcium phosphate porous bioceramic scaffold and preparation method thereof based on free extruded type 3D printing technique |
| CN109650909A (en) * | 2019-02-20 | 2019-04-19 | 四川大学 | A kind of calcium phosphate bone induction bioceramic scaffold and preparation method thereof based on photocuring 3D printing technique |
| CN110898256A (en) * | 2019-11-25 | 2020-03-24 | 四川大学 | Titanium metal-biological ceramic bone tissue engineering scaffold and preparation method thereof |
| CN111544644A (en) * | 2020-05-14 | 2020-08-18 | 广东省新材料研究所 | Calcium phosphate scaffold with multi-scale pore structure, preparation method and application |
| CN111803715A (en) * | 2020-07-17 | 2020-10-23 | 四川大学 | Degradable artificial bone particle with core-shell structure and preparation method thereof |
| CN112979303A (en) * | 2021-02-09 | 2021-06-18 | 浙江大学 | Bone tissue gradient scaffold with adjustable degradation speed and 3D printing-based forming method thereof |
| CN113292332A (en) * | 2021-06-11 | 2021-08-24 | 四川大学 | Calcium phosphate ceramic high-throughput screening model based on 3D printing, preparation method and application |
| CN114259604A (en) * | 2021-12-17 | 2022-04-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of 3D printing ordered vascularization promoting drug-loaded bone repair scaffold, product and application thereof |
| CN115042428A (en) * | 2022-06-07 | 2022-09-13 | 山东大学 | Additive manufacturing method for constructing multiple continuous gradient functional bone scaffold |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721740A (en) * | 2008-10-16 | 2010-06-09 | 上海国睿生命科技有限公司 | Bone tissue engineering bracket material and preparation method and application thereof |
| CN103877611A (en) * | 2014-04-08 | 2014-06-25 | 中山职业技术学院 | 3D printing preparation method of calcium phosphate-based medical bone tissue scaffold |
| WO2015021519A1 (en) * | 2013-08-12 | 2015-02-19 | Fundação Universidade Federal De São Carlos | Vitreous composition, bioactive vitreous fibres and fabrics, and articles |
| CN105582571A (en) * | 2016-02-24 | 2016-05-18 | 浙江大学 | Manufacturing method of high-strength bioactive porous scaffold |
| CN105769382A (en) * | 2016-02-24 | 2016-07-20 | 浙江大学 | Biological active porous structure support suitable for bone regeneration and repair and manufacturing method thereof |
-
2018
- 2018-02-07 CN CN201810121496.6A patent/CN108187149A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721740A (en) * | 2008-10-16 | 2010-06-09 | 上海国睿生命科技有限公司 | Bone tissue engineering bracket material and preparation method and application thereof |
| WO2015021519A1 (en) * | 2013-08-12 | 2015-02-19 | Fundação Universidade Federal De São Carlos | Vitreous composition, bioactive vitreous fibres and fabrics, and articles |
| CN103877611A (en) * | 2014-04-08 | 2014-06-25 | 中山职业技术学院 | 3D printing preparation method of calcium phosphate-based medical bone tissue scaffold |
| CN105582571A (en) * | 2016-02-24 | 2016-05-18 | 浙江大学 | Manufacturing method of high-strength bioactive porous scaffold |
| CN105769382A (en) * | 2016-02-24 | 2016-07-20 | 浙江大学 | Biological active porous structure support suitable for bone regeneration and repair and manufacturing method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109172044A (en) * | 2018-07-24 | 2019-01-11 | 西安交通大学 | A kind of degradable gradient-porosity mammary gland bracket |
| CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技（固安）有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
| CN109650872A (en) * | 2019-02-20 | 2019-04-19 | 四川大学 | A kind of calcium phosphate porous bioceramic scaffold and preparation method thereof based on free extruded type 3D printing technique |
| CN109650909A (en) * | 2019-02-20 | 2019-04-19 | 四川大学 | A kind of calcium phosphate bone induction bioceramic scaffold and preparation method thereof based on photocuring 3D printing technique |
| CN110898256A (en) * | 2019-11-25 | 2020-03-24 | 四川大学 | Titanium metal-biological ceramic bone tissue engineering scaffold and preparation method thereof |
| CN111544644A (en) * | 2020-05-14 | 2020-08-18 | 广东省新材料研究所 | Calcium phosphate scaffold with multi-scale pore structure, preparation method and application |
| CN111544644B (en) * | 2020-05-14 | 2022-08-26 | 广东省科学院新材料研究所 | Calcium phosphate scaffold with multi-scale pore structure, preparation method and application |
| CN111803715A (en) * | 2020-07-17 | 2020-10-23 | 四川大学 | Degradable artificial bone particle with core-shell structure and preparation method thereof |
| CN112979303A (en) * | 2021-02-09 | 2021-06-18 | 浙江大学 | Bone tissue gradient scaffold with adjustable degradation speed and 3D printing-based forming method thereof |
| CN113292332A (en) * | 2021-06-11 | 2021-08-24 | 四川大学 | Calcium phosphate ceramic high-throughput screening model based on 3D printing, preparation method and application |
| CN114259604A (en) * | 2021-12-17 | 2022-04-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of 3D printing ordered vascularization promoting drug-loaded bone repair scaffold, product and application thereof |
| CN115042428A (en) * | 2022-06-07 | 2022-09-13 | 山东大学 | Additive manufacturing method for constructing multiple continuous gradient functional bone scaffold |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108187149A (en) | A kind of controllable bone tissue engineering scaffold of degradation based on 3D printing and preparation method | |
| Ribas et al. | Current advances in bone tissue engineering concerning ceramic and bioglass scaffolds: A review | |
| Kumar et al. | Additive manufacturing methods for producing hydroxyapatite and hydroxyapatite-based composite scaffolds: a review | |
| CN111070376B (en) | 3D printing bionic porous bioceramic artificial bone and preparation method thereof | |
| CN105194728B (en) | A kind of degradable biological porous ceramic film material, preparation method and applications | |
| CN104710188B (en) | A kind of calcium-silicate biological ceramics porous material, preparation method and application | |
| KR100805303B1 (en) | Porous ceramic materials with various pore configuration and preparation thereof | |
| EP1429817B1 (en) | Porous ceramic composite bone grafts | |
| Sánchez-Salcedo et al. | Upgrading calcium phosphate scaffolds for tissue engineering applications | |
| Shepherd et al. | Calcium phosphate scaffolds for bone repair | |
| CN109650872A (en) | A kind of calcium phosphate porous bioceramic scaffold and preparation method thereof based on free extruded type 3D printing technique | |
| DE102006029298A1 (en) | Material system for 3D printing | |
| CN109260525A (en) | Controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing and preparation method thereof | |
| CN110304917B (en) | Barium titanate piezoelectric ceramic support for bone tissue engineering and preparation method thereof | |
| CN113101410B (en) | Tricalcium phosphate support with uniform mesopore and three-dimensional communicated hierarchical pore structure as well as preparation method and application of tricalcium phosphate support | |
| CN114452439B (en) | Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof | |
| CN110092653A (en) | A kind of degradable bata-tricalcium phosphate porous bioceramic scaffold of 3D printing and its preparation method and application | |
| CN105381505A (en) | 3D printing preparation method of bond defect repair stent | |
| CN105999400A (en) | CS/beta-TCP (calcium silicate/beta-tricalcium phosphate) porous composite material for promoting osteogenesis and vasculogenesis and preparation method thereof | |
| CN107050513A (en) | A kind of gradient dip-coating HA prepares ZrO2The method of Bone Defect Repari bioceramic scaffold material | |
| CN114404656A (en) | Core-shell structure fiber functional inorganic biomaterial, preparation method and application | |
| CN108530052A (en) | A method of utilizing gel effect 3D printing people's ceramic artificial bone | |
| CN113559326A (en) | Calcium silicate/magnesium silicate biological bone porous implant and preparation method and application thereof | |
| Cui et al. | Bioceramics: Materials, properties, and applications | |
| CN110898256A (en) | Titanium metal-biological ceramic bone tissue engineering scaffold and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180622 |