CN105233346A - Porous biological support slurry, three-dimensional porous biological support and preparation method of support - Google Patents

Porous biological support slurry, three-dimensional porous biological support and preparation method of support Download PDF

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CN105233346A
CN105233346A CN201510705376.7A CN201510705376A CN105233346A CN 105233346 A CN105233346 A CN 105233346A CN 201510705376 A CN201510705376 A CN 201510705376A CN 105233346 A CN105233346 A CN 105233346A
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biological support
slurry
dimensional porous
porous biological
support
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CN105233346B (en
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李亚运
熊信柏
曾燮榕
马俊
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Shenzhen University
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Shenzhen University
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Abstract

The invention discloses a porous biological support slurry, a three-dimensional porous biological support and a preparation method of the support. The porous biological support slurry comprises the following compositions: hydroxyapatite powder, zirconium oxide powder, a dispersant, a slurry stabilizing agent and a solvent. The three-dimensional porous biological support is formed by directly employing a direct-writing molding technology for processing the porous biological support slurry. The preparation method for the three-dimensional porous biological support comprises steps of preparing a direct-writing molded body, performing heat treatment on the body and the like. The porous biological support slurry possesses viscoelasticity response capable of being regulated and controlled and the shear thinning rheology characteristic, and therefore the slurry can be smoothly extruded and printed. The interior of the three-dimensional porous biological support shows periodic arrangement, and the whole three-dimensional porous biological support is a multi-layer cancellate stereo structure, the upper layer and the lower layer at the junction of the grid are in good connection, no accumulation collapse exist, the structure is complete, and the preparation method of the support enables a printed line to be capable of maintaining the line shape and a certain span even without any support, and is high in efficiency.

Description

Multiporous biological support slurry, three-dimensional porous biological support and preparation method thereof
Technical field
The invention belongs to medical material tech field, particularly a kind of multiporous biological support slurry for straight write forming, the three-dimensional porous biological support utilizing the straight write forming of described multiporous biological support slurry and preparation method thereof.
Background technology
The osseous tissue defect of human body is a kind of common disease, may be caused by factors such as skin injury, compromised internal and cancer surgery.Bone tissue engineer is exactly ultimate principle and the technology of using life sciences and engineering, manual simulation bone structure, and builds three-dimensional porous bioavailability bracket material, excites that inducing cell is bred on this support, the subject of skeletonization simultaneously.At present, hydroxyapatite (HAp) is most widely used material in lithotroph pottery, and its composition is similar to the inorganic constituents of skeleton with physicochemical property, has good biocompatibility, also has the effect of induction new bone formation.Three-dimensional porous hydroxyapatite structure is by a large amount of preparation for biomimic, but the shortcoming of the biological support of hydroxyapatite series is that fragility is comparatively large, comprcssive strength is low, can not repair human body hard tissue well.Zirconium oxide (ZrO 2) stable chemical nature of ceramic material, mechanical strength is high, simultaneously to cell, muscle and osseous tissue all without any toxic side effects.Zirconium powder is mixed with hydroxy apatite powder, the effect of toughness reinforcing hydroxyapatite structure can be played, improve the mechanical performance of porous support.
But current is generally that both mixture are adopted compression molding, then sintering processes, as hydroxyapatite and zirconium oxide are formed mixture is placed in mould exactly in Chinese patent CN1699270A, pressurizes and obtains biscuit, then is placed in high temperature furnace and fires.Also be that to adopt the mode of mold pressing to prepare with zirconium oxide be matrix central core at Chinese patent CN1709829A, and the mixing intermediate layer of the zirconium oxide spread respectively below thereon by different proportion mixing and hydroxyapatite, finally spread the surface layer of pure ha, form a kind of gradient laminated composite structure.
But because the situation of patient is different in clinical, also different to the requirement of the size and dimension of bioceramic scaffold, therefore, existing employing compression molding described above is wasted time and energy, and follow-up also need carries out a large amount of correction work to the support fired according to the concrete condition of patient, efficiency is low.
Occurred a kind of straight write forming technology in the recent period, it is a kind of novel 3D printing technique, and forming process, without any need for laser beam or ultraviolet radiation, also without the need to heating, at room temperature just can prepare three-dimensional complex shapes product by simple Ceramic Material.But adopting, the lines of blocking or the printing easily occurring slurry in straight write forming process are continuously imperfect, asymmetric, even occur unfavorable phenomenon generations such as subsiding.And current also discovery adopts straight write forming technology to print the relevant report of bioceramic scaffold.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of multiporous biological support slurry for straight write forming is provided, is only practically applicable to compression molding or adopts to print can not effectively be extruded or be extruded and the technical problem of stripe shape and span can not be maintained to solve existing multiporous biological support material.
Another object of the present invention is to the above-mentioned deficiency overcoming prior art, a kind of three-dimensional porous biological support and preparation method thereof is provided, adopt compression molding to waste time and energy to solve existing multiporous biological support material, the technical problem that production efficiency is low.
In order to realize foregoing invention object, as an aspect of of the present present invention, embodiments provide a kind of multiporous biological support slurry for straight write forming.The described component comprised for the multiporous biological support slurry of straight write forming has hydroxy apatite powder, Zirconium powder, dispersant and slurry stabilizing agent and solvent; Wherein, in described bioceramic scaffold slurry weight for 100%, the solid concentration of described bioceramic scaffold slurry is 30-60%wt, described dispersant is 0.5-1%wt, described stabiliser content is 0.5-1%wt, and described in have hydroxy apatite powder to account for described Zirconium powder and the described 50%-75% having hydroxy apatite powder gross weight.
As another aspect of the present invention, embodiments provide a kind of three-dimensional porous biological support.Described three-dimensional porous biological support adopts straight write forming technology to print by embodiment of the present invention multiporous biological support slurry and is formed.
Correspondingly, as another aspect of the present invention, embodiments provide a kind of preparation method of three-dimensional porous biological support.The preparation method of described three-dimensional porous biological support comprises the steps:
Convert three-dimensional porous biological support design drawing to computer discernible code language, along the path that computer is specified according to described code language, embodiment of the present invention multiporous biological support slurry is adopted the successively extrusion molding of straight write forming method, forms the base substrate of multilayer order three-dimensional porous network shape structure;
Described base substrate is removed the organic principle in described base substrate through super-dry, sintering processes.
Compared with prior art, the multiporous biological support slurry that the embodiment of the present invention is used for straight write forming is base material by hydroxy apatite powder and Zirconium powder, with dispersant and binding agent for adjuvant, and the consumption of each component is controlled, under realizing the effect of each component performance potentiation, the present embodiment is made to have the rheological charactristics of viscoelastic response and the shear shinning that can regulate and control for the multiporous biological support slurry of straight write forming, thus printing can be extruded smoothly, even and if can make print lines in without any support, also can maintain stripe shape and certain span, thus effectively can overcome existing multiporous biological support material and be only practically applicable to compression molding or adopt to print blocking easily occurs can not effectively be extruded or be extruded but lines are continuously imperfect, asymmetric, even there is unfavorable phenomenon generations such as subsiding.
The three-dimensional porous biological support of the embodiment of the present invention due to be utilize embodiment of the present invention multiporous biological support slurry adopt straight write forming technology print formed, therefore, its inside presents periodic arrangement, overall in Multilayer Network trellis stereochemical structure, connect good between intersection's levels of grid, subside without piling up, structural integrity, and distance between tie rods between lines and global shape and size can carry out accurately flexible modulation by structural design in advance.
The embodiment of the present invention three-dimensional porous biological support preparation method utilizes straight write forming technology by the direct printing shaping of embodiment of the present invention multiporous biological support slurry, therefore, accurately and flexibly can regulate and control pattern and the size of the three-dimensional porous biological support of preparation, effectively improve its production efficiency.And there is the rheological charactristics of viscoelastic response and the shear shinning that can regulate and control described above due to embodiment of the present invention multiporous biological support slurry, even if make the lines printed also can maintain stripe shape and certain span in without any support, the three-dimensional porous biological support inside of preparing is made to present periodic arrangement, overall in Multilayer Network trellis stereochemical structure, connect good between intersection's levels of grid, subside without piling up, structural integrity.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
The scanning electron microscope diagram sheet of the three-dimensional porous biological support that Fig. 1 is prepared according to the preparation method in three-dimensional porous biological support embodiment for the multiporous biological support slurry embodiment of the present invention 1 provided.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of multiporous biological support slurry for straight write forming with the rheological charactristics of viscoelastic response and the shear shinning that can regulate and control.In one embodiment, the component that embodiment of the present invention multiporous biological support slurry comprises has hydroxy apatite powder, Zirconium powder, dispersant and slurry stabilizing agent and solvent.
In embodiment of the present invention bioceramic scaffold slurry, described Zirconium powder and describedly have hydroxy apatite powder as base ingredients, has decisive action to the biology performance of embodiment of the present invention bioceramic scaffold slurry.Wherein, the composition of hydroxyapatite is similar to the inorganic constituents of skeleton with physicochemical property, has good biocompatibility, also has the effect of induction new bone formation.Zirconic stable chemical nature, mechanical strength is high, simultaneously to cell, muscle and osseous tissue all without any toxic side effects.In embodiments of the present invention Zirconium powder is mixed with hydroxy apatite powder, the effect of toughness reinforcing hydroxyapatite structure can be played, improve the mechanical performance of porous support.
In one embodiment, hydroxy apatite powder is had to account for described Zirconium powder and the described 50%-75% having hydroxy apatite powder gross weight described in control.
In another embodiment, the particle diameter controlling described Zirconium powder is 50-500nm, preferred 100-500nm.
In another embodiment, the particle diameter of hydroxy apatite powder is had to be 40-200nm described in control.
By both content control aforementioned proportion relations with to this above-mentioned scope of both particle diameters, can make on the one hand to ensure that the biological support of preparation has excellent biocompatibility and unload performance akin with bone, on the other hand, the multiporous biological support slurry viscoelastic response of the embodiment of the present invention for straight write forming and the rheological charactristics of shear shinning can be improved.
Above-mentioned dispersant can improve the dispersibility of each component contained by embodiment of the present invention multiporous biological support slurry, thus ensure the stability of embodiment of the present invention multiporous biological support slurry system, simultaneously with binder component effect, with the rheological charactristics of the viscoelastic response and shear shinning of improving slurry.Therefore,
In one embodiment, controlling the content of described dispersant in embodiment of the present invention multiporous biological support slurry system is 0.5-1%wt, in certain embodiments, this dispersant selects at least one in ammonium citrate, two citric acid monohydrate trisodiums, methylcellulose, Polyethylene Glycol, ammonium polyacrylate.
In another embodiment, controlling the content of described binding agent in embodiment of the present invention multiporous biological support slurry system is 0.5-1%wt, and in certain embodiments, at least one in polyvinyl alcohol (PVA), PVB selected by this binding agent.
Above-mentioned solvent can select medical acceptable solvent.In one embodiment, water selected by this solvent, as deionized water etc.Not only cost is low to select water, the more important thing is and can form stable water-based colloid slurry.
In straight write forming technology, preparation high-performance, stable slurry are the bases of forming process, are the key factors determining shaped article quality.The embodiment of the present invention with water as deionization be basic solvent to prepare gum size, its viscoelasticity can be regulated and controled within the scope of multiple order of magnitude, and forms the lines of pattern and span.
Therefore, multiporous biological support slurry be by control described Zirconium powder and described have a hydroxy apatite powder content and component particle diameter etc. therefore, effectively can give embodiment of the present invention multiporous biological support support prepared by slurry and there is good biocompatibility and the induction effect of new bone formation and the mechanical energy of excellence.By to described Zirconium powder, described in have the control of hydroxy apatite powder, dispersant and the constituent content such as slurry stabilizing agent and solvent and kind choosing then, give embodiment of the present invention multiporous biological support slurry and there is the viscoelastic response that can regulate and control on the one hand to ensure its extruding smoothly in print procedure, even and deposit to after on substrate and ensure also can maintain stripe shape and certain span without when any support below; On the other hand, slurry presents the rheological charactristics of good shear shinning, ensure that slurry can be extruded smoothly under the effect of shear stress.Thus effectively can overcome existing multiporous biological support material and be only practically applicable to compression molding or adopt to print blocking easily occurs can not effectively be extruded or be extruded but lines are continuously imperfect, asymmetric, the unfavorable phenomenon such as even occur subsiding occurs.
In addition, the preparation of the multiporous biological support slurry for straight write forming mentioned above, can take each component raw material according to the formula ratio above of slurry, each component is carried out mixing treatment.Wherein, before mixing treatment, preferably hydroxyapatite powder and Zirconium oxide powder are mixed, and be that this mixture is carried out ball-milling treatment by grinding aid with ethanol, 24h is placed on thermostatic drying chamber, obtains well-mixed Ceramic Material after 48h.
Can promote that powder body is dissolved into homogeneous system by supersonic vibration add dispersant, binding agent and solvent in the mixture of hydroxyapatite powder and Zirconium oxide powder after.
The another aspect of the embodiment of the present invention, the embodiment of the present invention additionally provides a kind of three-dimensional porous biological support, and described three-dimensional porous biological support embodiment of the present invention multiporous biological support slurry by mentioned earlier adopts straight write forming technology to print and formed.Therefore, its inside of the three-dimensional porous biological support of the embodiment of the present invention presents periodic arrangement, overall in Multilayer Network trellis stereochemical structure, connect good between intersection's levels of grid, subside without piling up, structural integrity, and distance between tie rods between lines and global shape and size can carry out accurately flexible modulation by structural design in advance.In addition, owing to being utilize straight write forming technology to print to be formed, therefore, the three-dimensional porous biological support of the embodiment of the present invention according to the real needs of patient, can also be related to shape and controlling dimension flexibly.
The another aspect of the embodiment of the present invention, the embodiment of the present invention additionally provides the preparation method of three-dimensional porous biological support mentioned above.In one embodiment, the preparation method of described three-dimensional porous biological support comprises the steps:
Step S01: convert three-dimensional porous biological support design drawing to computer discernible code language, along the path that computer is specified according to described code language, embodiment of the present invention multiporous biological support slurry mentioned above is adopted the successively extrusion molding of straight write forming technology, forms the base substrate of multilayer order three-dimensional porous network shape structure;
Step S02: described base substrate is removed the organic principle in described base substrate through super-dry, sintering processes.
Particularly, in above-mentioned steps S01, three-dimensional porous biological support design drawing is one of basis of whole straight write forming process.Straight write forming is based on the principle molding of discrete-superposition, and discrete additive process is roughly divided into that body is discrete, face is discrete and line is discrete.Body is discrete resolves into continuous print plane by 3D solid exactly, face discrete this be discrete for body go out tangent plane continue to be decomposed into a series of line segment for follow-up forming path, final step line is discrete, above-mentioned segment is divided into a series of entity point group, correspond to the minimum unit in molding.
In the process of the three-dimensional porous biological support of printing note inventive embodiments, straight write forming system is made up of three parts: be first computer software, completes the design of figure, and converts thereof into code language; Next is three-dimensional high-precision motion platform, the instruction that receiving computer sends, along the path movement designed in advance; Being finally slurry extrusion system, as formed by extruding syringe, air pressure regulator and gas cylinder, can providing that 1-70psi's extrude power.
Based on the principle of above-mentioned straight write forming system, the embodiment of the present invention adopts three-dimensional yard structure, and mutually orthogonal between its adjacent two layers, isotropism, with the three-dimensional porous biological support of printing note inventive embodiments.Particularly, first design the three-dimensional yard structure chart of the three-dimensional porous biological support of the embodiment of the present invention, then this three-dimensional yard structure chart is converted to computer discernible code language, instruction three-dimensional movement platform is moved according to code language intended trajectory with this code language by computer, thus carries out straight write forming.
Embodiment of the present invention multiporous biological support slurry mentioned above is inserted in slurry extrusion system, in one embodiment, embodiment of the present invention multiporous biological support slurry mentioned above is placed in the syringe that capacity is 10ml, select syringe needle internal diameter 0.4mm.After three-dimensional movement platform receives the instruction of computer, drive and extrude syringe along set orbiting motion, substrate deposits ground floor structure, then rises to suitable high shape second layer structure along Z axis, repeatedly carry out obtaining final three-dimensional yard structure blank.
In straight forming process, adjust corresponding extrusion pressure according to the rheological characteristic of slurry, making it drop on substrate can rapid solidification keep shape.The corresponding extrusion pressure of the slurry that viscosity is large is comparatively large, otherwise, then less.The movement velocity of syringe will match with extrusion pressure, and time movement velocity is little, corresponding extrusion pressure also will be turned down, and the too large slurry of pressure is extruded instantaneously and is too much deposited in some positions and will causes the asymmetric of total, even subsides.Time syringe needle movement velocity increases, extrusion pressure will tune up, otherwise pressure is too small, and slurry has little time to extrude, and homogeneous lines interrupt, and cause structure continuously imperfect.Therefore, according to the characteristic of embodiment of the present invention multiporous biological support slurry mentioned above, in one embodiment, in straight forming process in above-mentioned steps S01, controlling the speed that described multiporous biological support slurry prints is 3-5mm/s, and controlling the pressure that described multiporous biological support slurry is extruded is 40-60psi.To multiporous biological support slurry extrusion pressure and printing rate controlled, to coordinate the viscoelastic response of embodiment of the present invention multiporous biological support slurry excellence mentioned above and the rheological charactristics of shear shinning, slurry is enable to be extruded printing smoothly, even and if can make print lines in without any support, also can maintain stripe shape, continuous whole, and connect good between intersection's levels of grid, pile up without slurry and subside.
In another embodiment, the adjacent straight line in control same layer and the spacing of adjacent stems are 50-300 μm, and shank diameter is 50-300 μm.Make the multilayer order 3-D billet formed not only have porous network shape structure like this, there is excellent biocompatibility, and effectively can ensure the integrity of base substrate, avoid bad phenomenon such as subsiding.
In one embodiment, the base substrate width of the three-dimensional porous network shape structure that above-mentioned steps S01 is formed can be 5-15mm, highly can be 1-5mm.
In above-mentioned steps S02, step S01 formed base substrate through super-dry with solvent remaining in printed off site lines.After oversintering process, effectively go out organic substance, as removed the component such as dispersant and binding agent in embodiment of the present invention multiporous biological support slurry mentioned above.In one embodiment, the sintering processes in above-mentioned steps S02 comprises preheating and follow-up two stages of hyperpyrexia sintering processes.In a particular embodiment, be first by described base substrate pre-burning 1-2h at 100-200 DEG C, after with the heating rate of 100-200 DEG C/h to 1100-1250 DEG C of more than high temperature sintering 2h.By described sintering processes is arranged two stages, and the sintering process in each stage controls this scope, effectively can not only remove the organic substance in idiosome, hydroxy apatite powder and Zirconium powder can also be made to sinter, the synergistic effect of both performances, give the three-dimensional porous biological support excellence of preparation biocompatibility and with the near excellent mechanical ability of bone photo as toughness.Meanwhile, the three dimensional biological internal stent after sintering presents periodic arrangement, and overall structure is comparatively complete, and without significantly subsiding, bar cross section maintains good circle.
Below by way of multiple embodiment illustrate further illustrate above-mentioned for the multiporous biological support slurry of straight write forming, three-dimensional porous biological support and preparation method thereof.
Embodiment 1
A kind of multiporous biological support slurry for straight write forming of the present embodiment.Described multiporous biological support slurry (ceramic size) comprises hydroxy apatite powder and Zirconium powder mixing, thing ammonium citrate dispersant and PVA binding agent, hydroxy apatite powder content is the 50%wt of mixed powder, hydroxy apatite powder particle diameter is about 40-100nm, and Zirconium powder particle diameter is about 100-200nm; The content of described ammonium citrate dispersant in multiporous biological support slurry is 0.5%wt, and the content of described PVA binding agent in multiporous biological support slurry is 0.5%wt.
The solid concentration of described bioceramic scaffold slurry is 55%wt, and the solvent of slurry is deionized water.
The present embodiment 1 multiporous biological support slurry is before preparation, first is that hydroxy apatite powder and Zirconium powder mixture are carried out ball-milling treatment by grinding aid with ethanol, 24h is placed on thermostatic drying chamber, obtain well-mixed Ceramic Material after 48h, then to add in deionized water mixed being incorporated in remaining ingredient and shake ceramic size to stable homogeneous with ultrasonic cell disrupte machine.
Embodiment 2
A kind of multiporous biological support slurry (ceramic size) for straight write forming of the present embodiment.Described ceramic size comprises hydroxy apatite powder and Zirconium powder mixture, methylcellulose dispersant and PVB binding agent; Hydroxy apatite powder content is 60% of mixed powder, and hydroxy apatite powder particle diameter is about 100-150nm, and Zirconium powder particle diameter is about 200-300nm; Described methylcellulose dispersant is 1%wt, and described PVB binder content is 1%wt.
The solid concentration of described bioceramic scaffold slurry is 65%wt
The solvent of slurry is deionized water.
Embodiment 3
A kind of multiporous biological support slurry (ceramic size) for straight write forming of the present embodiment.Described ceramic size comprises hydroxy apatite powder and Zirconium powder mixture, Polyethylene Glycol dispersant and PVA binding agent; Hydroxy apatite powder content is 75% of mixed powder, and hydroxy apatite powder particle diameter is about 150-200nm, and Zirconium powder particle diameter is about 300-500nm.Described Polyethylene Glycol dispersant is 1%wt, and described PVA binder content is 1%wt.
The solid concentration of described bioceramic scaffold slurry is 70%wt, and the solvent of slurry is deionized water.
Three-dimensional porous biological support embodiment
Present embodiments provide a kind of three-dimensional porous biological support and preparation method thereof.This three-dimensional porous biological support adopts straight write forming technology to print by the multiporous biological support slurry provided in above-described embodiment 1 to be formed.
The present embodiment three-dimensional porous biological support preparation method is as follows:
Step S11: utilize CAD software to complete the three-dimensional structural graph design of three-dimensional porous biological support as required, then convert thereof into the discernible code language of computer;
Step S12: the multiporous biological support slurry provided in embodiment 1 is inserted and extrudes syringe, and along the path movement that computer is specified under the drive of three-dimensional platform, successively extrusion molding simultaneously, forms multilayer order three-dimensional porous network shape structure blank; Wherein, selecting syringe needle internal diameter 0.4mm, in the process of described extrusion molding, the speed (i.e. syringe needle rate travel) that described multiporous biological support slurry prints is 3-5mm/s, and the pressure that described multiporous biological support slurry is extruded is 40-60psi;
Step S13: the base substrate after molding is placed in low-temperature sintering stove pre-burning 1h at 200 DEG C, further solidification, then in high temperature sintering furnace, rise to 1200 DEG C of insulation 4h with the heating rate of 100 DEG C/h from room temperature and carry out sintering processes, cool to room temperature with the furnace and obtain three dimensional biological support.
Three dimensional biological support after sintering is characterized, use the internal structure of sem observation three dimensional biological support, as shown in Figure 1, can find out, sample interior after sintering presents periodic arrangement, overall structure is comparatively complete, and without significantly subsiding, cross section maintains well cylindrical; Filament lines diameter after sintering is about 300 μm.
The multiporous biological support slurry being used for straight write forming provided by embodiment 2-3 carries out shaped three dimensional multiporous biological support according to straight write forming technology respectively according to this three-dimensional porous biological support embodiment preparation method.Utilize scanning electron microscope to characterize respectively the three-dimensional porous biological support of preparation, observed result is learnt, even Fig. 1 of three-dimensional porous biological support pattern of preparation is similar to.All show inside and present periodic arrangement, overall structure is comparatively complete, and without significantly subsiding, bar cross section maintains good circle.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1., for a multiporous biological support slurry for straight write forming, the component comprised has hydroxy apatite powder, Zirconium powder, dispersant and slurry stabilizing agent and solvent; Wherein, in described bioceramic scaffold slurry weight for 100%, the solid concentration of described bioceramic scaffold slurry is 30-60%wt, described dispersant is 0.5-1%wt, described binder content is 0.5-1%wt, and described in have hydroxy apatite powder to account for described Zirconium powder and the described 50%-75% having hydroxy apatite powder gross weight.
2. multiporous biological support slurry as claimed in claim 1, is characterized in that: the rheological charactristics of described bioceramic scaffold slurry is shear shinning type.
3. multiporous biological support slurry as claimed in claim 1 or 2, is characterized in that: the particle diameter of described Zirconium powder is 50-500nm; And/or
Described have the particle diameter of hydroxy apatite powder to be 40-200nm.
4. multiporous biological support slurry as claimed in claim 1 or 2, is characterized in that: described dispersant is at least one in ammonium citrate, two citric acid monohydrate trisodiums, methylcellulose, Polyethylene Glycol, ammonium polyacrylate; And/or
Described binding agent is at least one in PVA, PVB.
5. a three-dimensional porous biological support, is characterized in that: described three-dimensional porous biological support adopts straight write forming technology to print by the arbitrary described multiporous biological support slurry of claim 1-4 and formed.
6. a preparation method for three-dimensional porous biological support, comprises the steps:
Convert three-dimensional porous biological support design drawing to computer discernible code language, along the path that computer is specified according to described code language, arbitrary for claim 1-4 described multiporous biological support slurry is adopted the successively extrusion molding of straight write forming technology, forms the base substrate of multilayer order three-dimensional porous network shape structure;
Described base substrate is removed the organic principle in described base substrate through super-dry, sintering processes.
7. preparation method as claimed in claim 6, is characterized in that: in the process of described extrusion molding, and the speed that described multiporous biological support slurry prints is 3-5mm/s, and the pressure that described multiporous biological support slurry is extruded is 40-60psi.
8. preparation method as claimed in claims 6 or 7, it is characterized in that: the adjacent stems spacing in described base substrate is 50-300 μm, shank diameter is 50-300 μm.
9. preparation method as claimed in claims 6 or 7, is characterized in that: the width of described base substrate is 5-15mm, is highly 1-5mm.
10. preparation method as claimed in claims 6 or 7, is characterized in that: described sintering processes comprises first by described base substrate pre-burning 1-2h at 100-200 DEG C, after with the heating rate of 100-200 DEG C/h to 1100-1250 DEG C of more than high temperature sintering 2h.
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CN109400200A (en) * 2018-11-30 2019-03-01 中南大学 A kind of macroscopical and all controllable hydroxyapatite porous ceramics and its preparation method and application of microstructure
CN109809810A (en) * 2019-03-07 2019-05-28 华南理工大学 A kind of bioactive ceramics bracket and preparation method thereof with heterogeneous porous bionical natural bony structure
CN109912303A (en) * 2019-04-24 2019-06-21 南京航空航天大学 A kind of calcium phosphate/zirconium oxide gradient porous support and preparation method and application
CN109939265A (en) * 2019-03-14 2019-06-28 杭州电子科技大学 3D printing method based on hydroxyapatite-zirconium dioxide artificial bone
CN111019068A (en) * 2019-12-25 2020-04-17 中国科学院兰州化学物理研究所 Polyimide photosensitive resin with extrudable shape memory performance and preparation and application thereof
CN111588906A (en) * 2019-02-21 2020-08-28 泽塔纳米科技(苏州)有限公司 SIC (SIC-reinforced hydroxyapatite) composite nano ceramic material and preparation method thereof
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CN109400200A (en) * 2018-11-30 2019-03-01 中南大学 A kind of macroscopical and all controllable hydroxyapatite porous ceramics and its preparation method and application of microstructure
CN109400200B (en) * 2018-11-30 2022-01-04 中南大学 Hydroxyapatite porous ceramic with controllable macro and micro structures and preparation method and application thereof
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