CN105439626A - Preparation method of porous calcium phosphate ceramic - Google Patents
Preparation method of porous calcium phosphate ceramic Download PDFInfo
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- CN105439626A CN105439626A CN201510850673.0A CN201510850673A CN105439626A CN 105439626 A CN105439626 A CN 105439626A CN 201510850673 A CN201510850673 A CN 201510850673A CN 105439626 A CN105439626 A CN 105439626A
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
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- 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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- 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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- 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
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Abstract
The invention discloses a preparation method of porous calcium phosphate ceramic and belongs to the field of biomaterials. According to the preparation method, a film-forming macromolecule is adopted as an organic pore-forming agent and matched with a water-soluble inorganic pore-forming agent, and the porous calcium phosphate ceramic is obtained with a multi-stage pore-forming technology. The method combines organic and inorganic pore-forming agents and performs multi-stage pore formation, the prepared porous calcium phosphate ceramic has a multi-stage communicated pore structure of small pores sleeved with large pores, and the porosity and the pore size are controllable. The film-forming macromolecule is adopted as the organic pore-forming agent, on one hand, fixation and formation of calcium phosphate powder and the inorganic pore-forming agent are facilitated by the aid of the film-forming characteristic of the film-forming macromolecule, on the other hand, the organic pore-forming agent after film formation constitutes an intercommunicated organic framework of a ceramic body and plays roles in supporting and fixing the body, and meanwhile, the intercommunicated pore structure can be left in the ceramic after the organic pore-forming agent is removed at the high temperature.
Description
Technical field
The invention belongs to technical field of biological material, be specifically related to a kind of preparation method of porous calcium phosphate ceramic.
Technical background
Clinical medicine shows, autologous bone, allogenic bone transplantation are the main method for the treatment of bone tissue restoration, but its bone limited source, also there is the problem such as immunological rejection and pathophoresis, application is very limited.Therefore find the equivalent material with the artificial bone tissue of similar action and just seem quite important.
Bone tissue restoration its depend primarily on complementary surface reaction mechanism between material and biological tissue, be combined with tissue cross by the mutual interaction of the multiple binding mechanism between material and biological tissue, reach the reparation object of osseous tissue.According to bone tissue engineer principle, porous bio-ceramic, the calcium phosphorus system porous bio-ceramic especially with biodegradation character is the ideal material of bone defect healing, but the distribution of its aperture size, porosity and mechanical strength are difficult to well matched.Human body can load bone mechanical strength at about 4 ~ 12MPA, and at present the calcium phosphate porous ceramic mechanical strength with the distribution of better aperture size and porosity of main flow is not high, at 1 ~ 2MPA; Mechanical strength high and can meet that load bone Repair strength requires, its pore size distribution is uneven or connectivity is poor.
Summary of the invention
Based on the contradictory problems of above hole dimension, porosity and mechanical strength, the present invention is to provide a kind of method preparing porous calcium phosphate ceramic in conjunction with the multistage drilling of organic-inorganic perforating agent.Porous calcium phosphate ceramic prepared by the method has controlled porosity and can reach high value, and the multistage drilling of organic-inorganic perforating agent obtains controlled and homogeneous aperture size, good connectivity and mechanical strength.
The present invention is achieved through the following technical solutions:
A preparation method for porous calcium phosphate ceramic, adopts film-forming properties polymer as organic perforating agent hydrous water insoluble inorganic perforating agent, obtains porous calcium phosphate ceramic by multistage drill process.The method is in conjunction with organic and inorganic perforating agent and carry out multistage drilling, and the porous calcium phosphate ceramic prepared has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.Film-forming properties polymer is adopted to utilize its film forming characteristics to be conducive to being fixed with shaping to calcium phosphate powder and inorganic perforating agent on the one hand as organic perforating agent, on the other hand, organic perforating agent after film forming forms the mutually through organic backbone of ceramic body, support fixed action is played to base substrate, mutually through pore structure can be left in pottery simultaneously after organic perforating agent is at high temperature removed.
Alternately, in above-mentioned preparation method, described film-forming properties polymer is at least one in poly(lactic acid), chitosan, Mierocrystalline cellulose, polyimide, polystyrene.These polymers have good film-forming properties, are conducive to forming base substrate smoothly when solvent flashing.
Alternately, in above-mentioned preparation method, described inorganic perforating agent is the inorganic perforating agent simultaneously with good water-soluble and thermal decomposition characteristic.In base substrate, cavity is formed after well water-soluble makes inorganic perforating agent and water contact lysis, form the macroporous structure in multistage intercommunicating pore structure, good inorganic perforating agent makes a small amount of inorganic perforating agent decomposes in sintering process of dissolving rear remnants, forms the part connectivity structure between Kong Yukong and the micro-nano pore structure on large hole wall.The particle diameter of described inorganic perforating agent can be selected flexibly according to the design requirements of ceramic macropore diameter, preferably 300 ~ 500 microns.
Alternately, in above-mentioned preparation method, described inorganic perforating agent is at least one in bicarbonate of ammonia, volatile salt, sodium bicarbonate.More elect bicarbonate of ammonia as, its thermal decomposition product is all discharged as gas, and thing is any residual in the product.
Alternately, in above-mentioned preparation method, by described film-forming properties macromolecule dissolution in volatile solvent, then calcium phosphate powder and the mixing of water-soluble inorganic perforating agent is added, leave standstill volatilization and obtain block materials except desolventizing, block materials is put into boiling water, removes inorganic perforating agent, then sinter porcelain into and in sintering process, remove residual mineral perforating agent and organic perforating agent simultaneously, obtain porous calcium phosphate ceramic.
Alternately, in above-mentioned preparation method, described volatile solvent is the mixing solutions of in acetone, chloroform, ethanol at least two kinds.Adopt this several solvent or its mixing solutions to be conducive to the high molecular dissolving of film-forming properties, and in volatilization process, be conducive to organic perforating agent film forming fixing formation base substrate.
Alternately, in above-mentioned preparation method, described calcium phosphate is at least one in monocalcium phosphate (DCPD), tricalcium phosphate (α-TCP and β-TCP), hydroxyapatite (HA), tetracalcium phosphate (TTCP), biphasic calcium phosphate (BCP).
Alternately, in above-mentioned preparation method, described sintering temperature is 800 ~ 1300 DEG C.
Alternately, in above-mentioned preparation method, concrete steps are as follows:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent, the solution of configuration 0.1 ~ 0.5g/ml, ultrasonic agitation mixes;
A3, join in solution by the inorganic perforating agent of calcium phosphate powder and certain particle diameter, ultrasonic agitation, mixes;
B, shaping
A3 gained solution is left standstill volatilization at-20 ~-5 DEG C, obtains the block materials after organic solvent volatilization completely;
C, drilling
The block materials of B gained is put into boiling water soak, remove inorganic perforating agent;
D, high temperature sintering
By C gained sample, 800 ~ 1300 degree of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous calcium phosphate ceramic.
Alternately, in above-mentioned preparation method, the film-forming properties polymer of described steps A 2 is the mixture of poly(lactic acid)/polystyrene or the mixture (poly(lactic acid)/polystyrene mass ratio 1:1, Mierocrystalline cellulose/polyimide mass ratio 1:2) of Mierocrystalline cellulose/polyimide.
Alternately, in above-mentioned preparation method, in described steps A 2, the concentration of film-forming properties macromolecular solution is 0.2g/ml.
Alternately, in above-mentioned preparation method, in described steps A 3, the ratio of calcium phosphate powder and inorganic perforating agent can adjust flexibly according to the porosity of product, and preferred volume ratio is 1:0.8 ~ 1:3.
Alternately, in above-mentioned preparation method, leave standstill volatilization in described step B and carry out at-10 DEG C, time of repose is 5 ~ 7 days.
Alternately, in above-mentioned preparation method, the time that in described step C, boiling water soaks is 2 ~ 10 hours, is preferably 5 hours.
Present invention also offers a kind of porous calcium phosphate ceramic adopting aforesaid method to prepare, it is characterized in that, described porous calcium phosphate ceramic has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.
Alternately, the self-bone grafting that above-mentioned porous calcium phosphate ceramic is good and osteoconductive nature.
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Beneficial effect of the present invention:
1, with existing research the mode of directly adding pore-forming material or particle packing is passed through, and the timbering material that the mode of gas foaming obtains is compared, using organic-inorganic perforating agent to combine multistage drilling, can to obtain connectivity better, the timbering material that aperture is more controlled and homogeneous, wherein organic polymer drilling can obtain more how nanometer level microporous, the inorganic perforating agent of certain particle diameter can obtain controlled homogeneous micron order macropore, is conducive to the biological activity and the osteoinductive that improve support.Controlled micro/nano level hierarchical porous structure Effective Regulation support mechanical structure, makes support intensity be improved.
2, compared with the timbering material obtained by the mode of volume extrusion molding in existing research, can better promote that dispersion of materials is even by organic solution ultrasonic vibration mixed powder and perforating agent.
Accompanying drawing illustrates:
Fig. 1 is scanning electron microscope (SEM) photo of the porous HA pottery of preparation in the embodiment of the present invention 1, and magnification is 100 times.
Fig. 2 is scanning electron microscope (SEM) photo of the porous HA pottery of preparation in the embodiment of the present invention 1, and magnification is 5000 times.
Fig. 3 is scanning electron microscope (SEM) photo of the porous HA pottery of preparation in the embodiment of the present invention 1, and magnification is 20000 times.
Embodiment:
Embodiment is by the following examples described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Not departing from any amendment made within the spirit and principles in the present invention, and the equivalent replacement made according to ordinary skill knowledge and customary means or improvement, all should be included in protection scope of the present invention.
Embodiment 1
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.2g/ml, ultrasonic agitation mixes;
A3, by hydroxyapatite (HA) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:2 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery.
Embodiment 2
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.1g/ml, ultrasonic agitation mixes;
A3, by tricalcium phosphate (α-TCP) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:0.8 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-20 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 7 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 800 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous α-TCP pottery.
Embodiment 3
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by tricalcium phosphate (β-TCP) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:2 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-5 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 6 days.
C, drilling
The block materials of B gained is put into boiling water 2 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous beta-TCP pottery.
Embodiment 4
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by biphasic calcium phosphate (BCP) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:3 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-20 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 10 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous BCP pottery.
Embodiment 5
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by tetracalcium phosphate (TTCP) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:2 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous TTCP pottery.
Embodiment 6
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-chloroform mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent (poly(lactic acid)/polystyrene mass ratio 1:1), the solution of configuration 0.2g/ml, ultrasonic agitation mixes;
A3, by hydroxyapatite (HA) powder and size distribution 300 ~ 500 microns inorganic perforating agent volatile salt by volume ratio 1:3 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery.
Embodiment 7
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-ethanol mixing solutions of A1, configuration volume ratio 1:2;
A2, join in solution using film-forming properties polymer as organic perforating agent (Mierocrystalline cellulose/polyimide mass ratio 1:2), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by hydroxyapatite (HA) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:2 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery.
Embodiment 8
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-ethanol mixing solutions of A1, configuration volume ratio 1:2;
A2, join in solution using film-forming properties polymer as organic perforating agent (Mierocrystalline cellulose/polyimide mass ratio 1:2), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by hydroxyapatite (HA) powder and size distribution 300 ~ 500 microns inorganic perforating agent sodium bicarbonate by volume ratio 2:1 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery.
Embodiment 9
Prepare porous calcium phosphate ceramic according to the following steps:
Prepared by A, solution:
The acetone-ethanol mixing solutions of A1, configuration volume ratio 1:2;
A2, join in solution using film-forming properties polymer as organic perforating agent (Mierocrystalline cellulose/polyimide mass ratio 1:2), the solution of configuration 0.5g/ml, ultrasonic agitation mixes;
A3, by monocalcium phosphate (DCPD) powder and size distribution 300 ~ 500 microns inorganic perforating agent bicarbonate of ammonia by volume ratio 1:2 join in solution, ultrasonic agitation, mixes.
B, shaping
Be placed in 15ml small beaker by A3 gained solution ,-10 DEG C leave standstill volatilization.The block materials after organic solvent volatilization is completely obtained after 5 days.
C, drilling
The block materials of B gained is put into boiling water 5 hours, remove inorganic perforating agent.
D, high temperature sintering
By C gained sample, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous calcium phosphate calcium dihydrogen pottery.
Scanning electronic microscope and omnipotent mechanics machine is adopted to characterize the porous calcium phosphate ceramic of gained in the various embodiments described above respectively, result shows: the ultimate compression strength of the porous calcium phosphate ceramic of each embodiment gained is all not less than 4MPa, all there is the multistage intercommunicating pore structure of large borehole jack aperture, and its porosity and pore size adjust and accurately control flexibly by adjusting the parameters such as the additional proportion of the size distribution of calcium phosphate powder, calcium phosphate powder and pore-creating agent.Fig. 1-3 is respectively the stereoscan photograph of porous HA pottery under three kinds of different amplification described in embodiment 1, the abundant macropore of 100 ~ 500 microns is contained as seen from the figure in described porous HA pottery, be interconnected by aperture between macropore, containing abundant micropore (<20 μm) on large hole wall.
Embodiment 10
In above-mentioned any embodiment, change the mixing solutions in steps A 1 in acetone, chloroform, ethanol at least one, organic perforating agent in steps A 2 is changed at least one in poly(lactic acid), chitosan, Mierocrystalline cellulose, polyimide, polystyrene, inorganic perforating agent in steps A 3 is changed at least one in bicarbonate of ammonia, volatile salt, sodium bicarbonate, all successfully can prepare porous calcium phosphate ceramic, the porous calcium phosphate ceramic of gained all has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.Comparing result shows: when other conditions are identical, selects the mixing solutions of in acetone, chloroform, ethanol at least two kinds to be more conducive to the high molecular dissolving of film-forming properties, and in volatilization process, be conducive to organic perforating agent film forming fixing formation base substrate; When other conditions are identical, select the mixture of poly(lactic acid)/polystyrene or the mixture of Mierocrystalline cellulose/polyimide to be more conducive to film forming and fix; When other conditions are identical, select bicarbonate of ammonia to do inorganic perforating agent effect better, its thermal decomposition product is all discharged as gas, and thing is any residual in the product.
Embodiment 11
The ratio mixed dissolution of Mierocrystalline cellulose and polyimide 1:2 is in mass ratio mixed with in the mixed solvent (volume ratio 1:2) of volatile solvent acetone and ethanol the solution of 0.5g/ml, then calcium phosphate powder and saleratus mixing that volume ratio is 1:1 is added, leave standstill at-15 DEG C and volatilize except desolventizing obtains block materials, block materials is put into boiling water to soak 2 hours, remove inorganic perforating agent, then sinter porcelain into and in sintering process, remove residual mineral perforating agent and organic perforating agent simultaneously, obtain porous calcium phosphate ceramic.
The pore texture of gained pottery is similar to the HA porous ceramics of gained in the present embodiment to mechanical property, and the porous calcium phosphate ceramic of gained all has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.
Embodiment 12
Chitosan is dissolved in the solution being mixed with 0.1g/ml in volatile solvent ethanol, then calcium phosphate powder and sodium bicarbonate mixing that volume ratio is 0.8:1 is added, leave standstill at-5 DEG C and volatilize except desolventizing obtains block materials, block materials is put into boiling water to soak 10 hours, remove inorganic perforating agent, then sinter porcelain into and in sintering process, remove residual mineral perforating agent and organic perforating agent simultaneously, obtain porous calcium phosphate ceramic.
The pore texture of gained pottery is similar to the HA porous ceramics of gained in the present embodiment to mechanical property, and the porous calcium phosphate ceramic of gained all has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.
Embodiment 13
The ratio mixed dissolution of Mierocrystalline cellulose and polyimide 2:1 is in mass ratio mixed with in the mixed solvent (volume ratio 2:1) of volatile solvent chloroform and ethanol the solution of 0.4g/ml, then calcium phosphate powder and bicarbonate of ammonia mixing that volume ratio is 1:2 is added, leave standstill at-20 DEG C and volatilize except desolventizing obtains block materials, block materials is put into boiling water to soak 7 hours, remove inorganic perforating agent, then sinter porcelain into and in sintering process, remove residual mineral perforating agent and organic perforating agent simultaneously, obtain porous calcium phosphate ceramic.
The pore texture of gained pottery is similar to the HA porous ceramics of gained in the present embodiment to mechanical property, and the porous calcium phosphate ceramic of gained all has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.
Embodiment 14 and co-culture of cells
Get the porous calcium phosphate ceramic block prepared in above-mentioned any embodiment, cut into and be of a size of F12*2mm disc-shaped porous support, this porous support is placed in 75% alcohol soaked overnight, the PBS solution cleaning of sterilizing is placed in 24 well culture plates, by every sheet material 2 × 10
4bone Marrow Mesenchymal Stem Cells of Mice (MSCs) cell is seeded on porous support materials by the inoculum density of individual cell, is placed in 37 DEG C/5%CO
2cell cultures is carried out in cell culture incubator; Cell cultures 3 days poststainings, observe the growing state of MSCs on POROUS TITANIUM surface by laser confocal microscope (CLSM), result showed cell attaches well-grown at material surface, shows that this porous titanium material has good biocompatibility.
Claims (10)
1. a preparation method for porous calcium phosphate ceramic, is characterized in that, adopts film-forming properties polymer as organic perforating agent hydrous water insoluble inorganic perforating agent, obtains porous calcium phosphate ceramic by multistage drill process.
2. the preparation method of porous calcium phosphate ceramic according to claim 1, is characterized in that, described film-forming properties polymer is at least one in poly(lactic acid), chitosan, Mierocrystalline cellulose, polyimide, polystyrene.
3. the preparation method of porous calcium phosphate ceramic according to claim 1, is characterized in that, described inorganic perforating agent is the inorganic perforating agent simultaneously with good water-soluble and thermal decomposition characteristic.
4. the preparation method of porous calcium phosphate ceramic according to claim 1, is characterized in that, described inorganic perforating agent is at least one in bicarbonate of ammonia, volatile salt, sodium bicarbonate.
5. the preparation method of porous calcium phosphate ceramic according to claim 1, it is characterized in that, by described film-forming properties macromolecule dissolution in volatile solvent, then calcium phosphate powder and the mixing of water-soluble inorganic perforating agent is added, leave standstill volatilization and obtain block materials except desolventizing, block materials is put into boiling water, removes inorganic perforating agent, then sinter porcelain into and in sintering process, remove residual mineral perforating agent and organic perforating agent simultaneously, obtain porous calcium phosphate ceramic.
6. the preparation method of porous calcium phosphate ceramic according to claim 5, is characterized in that, described volatile solvent is the mixing solutions of in acetone, chloroform, ethanol at least two kinds.
7. the preparation method of porous calcium phosphate ceramic according to claim 5, it is characterized in that, described calcium phosphate is at least one in tricalcium phosphate (α-TCP and β-TCP), hydroxyapatite (HA), tetracalcium phosphate, monocalcium phosphate.
8. the preparation method of porous calcium phosphate ceramic according to claim 5, is characterized in that, described sintering temperature is 800 ~ 1300 DEG C.
9. the preparation method of porous calcium phosphate ceramic according to claim 5, is characterized in that, concrete steps are as follows:
Prepared by A, solution:
The organic solvent mixing solutions of A1, configuration volume ratio 1:1;
A2, join in solution using film-forming properties polymer as organic perforating agent, the solution of configuration 0.1 ~ 0.5g/ml, ultrasonic agitation mixes;
A3, joined in proportion in solution by the inorganic perforating agent of calcium phosphate powder and certain particle diameter, ultrasonic agitation, mixes;
B, shaping
A3 gained solution is left standstill volatilization at-20 ~-5 DEG C, obtains the block materials after organic solvent volatilization completely;
C, drilling
The block materials of B gained is put into boiling water soak, remove inorganic perforating agent;
D, high temperature sintering
By C gained sample, 800 ~ 1300 degree of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous calcium phosphate ceramic.
10. the porous calcium phosphate ceramic prepared of method according to claim 1, it is characterized in that, described porous calcium phosphate ceramic has the multistage intercommunicating pore structure of large borehole jack aperture, porosity and pore size controlled, ultimate compression strength is not less than 4MPa.
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