CN105439626B - A kind of preparation method of porous calcium phosphate ceramic - Google Patents
A kind of preparation method of porous calcium phosphate ceramic Download PDFInfo
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- CN105439626B CN105439626B CN201510850673.0A CN201510850673A CN105439626B CN 105439626 B CN105439626 B CN 105439626B CN 201510850673 A CN201510850673 A CN 201510850673A CN 105439626 B CN105439626 B CN 105439626B
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- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/12—Phosphorus-containing materials, e.g. apatite
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Abstract
The invention discloses a kind of preparation method of porous calcium phosphate ceramic, belong to technical field of biological material.The preparation method coordinates water-soluble inorganic perforating agent using film forming macromolecule as organic perforating agent, and porous calcium phosphate ceramic is obtained by multistage drill process.This method combines organic and inorganic perforating agent and carries out multistage drilling, and the porous calcium phosphate ceramic prepared has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable.Using its film forming characteristics be conducive to that calcium phosphate powder and inorganic perforating agent are fixed and be molded as organic perforating agent one side using film forming macromolecule, on the other hand, organic perforating agent after film forming forms the organic backbone being mutually communicated of ceramic body, support fixation is played to base substrate, while the pore structure being mutually communicated can be left in ceramics after organic perforating agent is removed at high temperature.
Description
Technical field
The invention belongs to technical field of biological material, and in particular to a kind of preparation method of porous calcium phosphate ceramic.
Technical background
Clinical medicine shows, autologous bone, allogenic bone transplantation are the main methods for treating bone tissue reparation, but its bone source
It is limited, also there are the problems such as immunological rejection and transmission, using being very limited.Therefore finding has similar action
The alternative materials of artificial bone tissue just seem quite important.
It depends primarily upon complementary interfacial reaction mechanism between material and living tissue to bone tissue reparation, passes through material
The effect that interacts of a variety of binding mechanisms between material and living tissue intersects combination with tissue, reaches the reparation mesh of bone tissue
's.According to bone tissue engineer principle, porous bio-ceramic, the calcium phosphorus system porous bio-ceramic especially with biodegradation character
It is the ideal material of bone defect healing, but its aperture size is distributed, porosity and mechanical strength are difficult to mate to very well.Human body
Can load-bearing bone mechanical strength in 4~12MPA or so, and at present mainstream have preferable aperture size distribution and porosity phosphoric acid
Calcium porous ceramics mechanical strength is not high, in 1~2MPA；Mechanical strength is high and can meet load-bearing bone Repair strength requirement, its
Pore-size distribution is uneven or connectivity is poor.
The content of the invention
Based on the contradictory problems of above pore size, porosity and mechanical strength, the present invention is to provide a kind of with reference to organic nothing
The method that machine perforating agent multistage drilling prepares porous calcium phosphate ceramic.Porous calcium phosphate ceramic prepared by this method has controllable
Porosity can simultaneously reach high value, and organic-inorganic perforating agent multistage drilling obtains controllable and homogeneous aperture size, good
Connectivity and mechanical strength.
The present invention is achieved through the following technical solutions：
A kind of preparation method of porous calcium phosphate ceramic, coordinates water solubility using film forming macromolecule as organic perforating agent
Inorganic perforating agent, porous calcium phosphate ceramic is obtained by multistage drill process.This method combines organic and inorganic perforating agent and carries out
Multistage drilling, the porous calcium phosphate ceramic prepared have the multistage intercommunicating pore structure of macropore set aperture, and porosity and aperture are big
Small controllable, compression strength is not less than 4MPa.On the one hand its film forming characteristics is utilized as organic perforating agent using film forming macromolecule
Be conducive to that calcium phosphate powder and inorganic perforating agent are fixed and be molded, on the other hand, organic perforating agent after film forming is formed
The organic backbone being mutually communicated of ceramic body, plays base substrate support fixation, while works as organic perforating agent at high temperature
The pore structure being mutually communicated can be left after being removed in ceramics.
Alternately, in above-mentioned preparation method, the film forming macromolecule is polylactic acid, chitosan, fiber
At least one of element, polyimides, polystyrene.These macromolecules have good film forming, are conducive in solvent flashing
When smoothly form base substrate.
Alternately, in above-mentioned preparation method, the inorganic perforating agent for have at the same time good water solubility and
The inorganic perforating agent of thermal decomposition characteristic.Good water solubility make it that inorganic perforating agent is empty with being formed after water contact lysis in base substrate
Hole, forms the macroporous structure in multistage intercommunicating pore structure, and good inorganic perforating agent causes a small amount of no mechanism remaining after dissolving
Hole agent is thermally decomposed in sintering process, forms the part connectivity structure between Kong Yukong and the micro-nano hole knot on big hole wall
Structure.The particle diameter of the inorganic perforating agent can flexibly be selected according to the design requirement of ceramic macropore diameter, preferably 300 ~ 500 microns.
Alternately, in above-mentioned preparation method, the inorganic perforating agent is ammonium hydrogen carbonate, ammonium carbonate, bicarbonate
At least one of sodium.More elect ammonium hydrogen carbonate as, its thermal decomposition product is all discharged as gas, and thing is any residual in the product
Stay.
Alternately, in above-mentioned preparation method, by the film forming macromolecule dissolution in volatile solvent, so
Calcium phosphate powder is added afterwards and water-soluble inorganic perforating agent mixes, and is stood volatilization removing solvent and is obtained block materials, by block material
Material be put into boiling water, remove inorganic perforating agent, then sinter into porcelain at the same time in sintering process remove residual mineral perforating agent and
Organic perforating agent, obtains porous calcium phosphate ceramic.
Alternately, in above-mentioned preparation method, the volatile solvent is acetone, at least two in chloroform, ethanol
The mixed solution of kind.The high molecular dissolving of film forming is conducive to using these types of solvent or its mixed solution, and in volatilization process
In be conducive to the film forming fixation of organic perforating agent and form base substrate.
Alternately, in above-mentioned preparation method, the calcium phosphate is calcium dihydrogen phosphate (DCPD), tricalcium phosphate
At least one of (α-TCP and β-TCP), hydroxyapatite (HA), tetracalcium phosphate (TTCP), biphasic calcium phosphate (BCP).
Alternately, in above-mentioned preparation method, the sintering temperature is 800~1300 DEG C.
Alternately, in above-mentioned preparation method, comprise the following steps that：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, be added to film forming macromolecule as organic perforating agent in solution, configures the solution of 0.1~0.5g/ml, surpasses
Sound is uniformly mixed；
The inorganic perforating agent of calcium phosphate powder and certain particle diameter, be added in solution by A3, is stirred by ultrasonic, and is uniformly mixed；
B, it is molded
A3 resulting solutions are stood to volatilization at -20 ~ -5 DEG C, obtain the block materials after organic solvent volatilization completely；
C, drilling
Block materials obtained by B are put into boiling water and are soaked, remove inorganic perforating agent；
D, high temperature sintering
By sample obtained by C, 800~1300 degree of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain more
Hole calcium phosphate ceramic.
Alternately, in above-mentioned preparation method, the film forming macromolecule of the step A2 is polylactic acid/polyphenyl second
The mixture of alkene or the mixture (polylactic acid/polystyrene mass ratio 1 of cellulose/polyimides:1, cellulose/polyimides
Mass ratio 1:2).
Alternately, in above-mentioned preparation method, the concentration of film forming Polymer Solution is in the step A2
0.2g/ml。
Alternately, in above-mentioned preparation method, the ratio of calcium phosphate powder and inorganic perforating agent in the step A3
Example can be adjusted flexibly according to the porosity of product, preferred volume ratio 1:0.8~1：3.
Alternately, stand volatilization in above-mentioned preparation method, in the step B to carry out at -10 DEG C, during standing
Between be 5 ~ 7 days.
Alternately, it is excellent when the time that boiling water soaks in the step C is 2 ~ 10 small in above-mentioned preparation method
Elect as 5 it is small when.
Present invention also offers a kind of porous calcium phosphate ceramic prepared using the above method, it is characterised in that described more
Hole calcium phosphate ceramic has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable, and compression strength is not small
In 4MPa.
Alternately, the good self-bone grafting of above-mentioned porous calcium phosphate ceramic and osteoconductive nature.
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Beneficial effects of the present invention：
1st, with existing research directly adding pore creating material either by way of particle packing, and the side of gas foaming
The timbering material that formula obtains is compared, and combining multistage drilling using organic-inorganic perforating agent can obtain that connectivity is more preferable, and aperture is more
Controllable and homogeneous timbering material, wherein organic polymer drilling can obtain it is more nanometer level microporous, certain particle diameter without mechanism
Hole agent can obtain controllable homogeneous micron order macropore, be conducive to improve the bioactivity and osteoinductive of stent.Controllable micro-nano
Meter level hierarchical porous structure Effective Regulation stent mechanical structure, is improved support intensity.
2nd, compared with the timbering material obtained in existing research by way of volume extrusion forming, surpassed by organic solution
Mixed powder and perforating agent are swung in acoustic shock preferably to promote material to be uniformly dispersed.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope of the porous HA ceramics prepared in the embodiment of the present invention 1（SEM）Photo, amplification factor 100
Times.
Fig. 2 is the scanning electron microscope of the porous HA ceramics prepared in the embodiment of the present invention 1（SEM）Photo, amplification factor are
5000 times.
Fig. 3 is the scanning electron microscope of the porous HA ceramics prepared in the embodiment of the present invention 1（SEM）Photo, amplification factor are
20000 times.
Embodiment：
Embodiment by the following examples is again described in further detail the above of the present invention.But
The scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following example.The spiritual and former of the present invention is not being departed from
Any modification made within then, and the equivalent substitution made according to ordinary skill knowledge and customary means or change
Into should all include within the scope of the present invention.
Embodiment 1
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.2g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by hydroxyapatite（HA）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:2 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery
Porcelain.
Embodiment 2
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.1g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by tricalcium phosphate（α-TCP）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:0.8 is added in solution, is stirred by ultrasonic, and is uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -20 DEG C stand volatilization.Organic solvent is obtained after 7 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 800 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous α-TCP
Ceramics.
Embodiment 3
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by tricalcium phosphate（β-TCP）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:2 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -5 DEG C stand volatilization.It is complete that organic solvent volatilization is obtained after 6 days
Block materials afterwards.
C, drilling
By the block materials obtained by B be put into boiling water 2 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1300 DEG C of high temperature sinterings remove residual mineral perforating agents and organic perforating agent, obtain porous beta-
TCP ceramics.
Embodiment 4
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by biphasic calcium phosphate（BCP）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:3 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -20 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 10 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous BCP
Ceramics.
Embodiment 5
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by tetracalcium phosphate（TTCP）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:2 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous TTCP
Ceramics.
Embodiment 6
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1：1 acetone-chloroform mixed solution；
A2, using film forming macromolecule as organic perforating agent (polylactic acid/polystyrene mass ratio 1:1) it is added to solution
In, the solution of 0.2g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by hydroxyapatite（HA）Powder and particle diameter distribution press body in 300 ~ 500 microns of inorganic perforating agent ammonium carbonate
Product ratio 1:3 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery
Porcelain.
Embodiment 7
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1:2 acetone-ethanol mixed solution；
A2, using film forming macromolecule as organic perforating agent (cellulose/polyimides mass ratio 1:2) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by hydroxyapatite（HA）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent ammonium hydrogen carbonate
Volume ratio 1:2 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery
Porcelain.
Embodiment 8
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1:2 acetone-ethanol mixed solution；
A2, using film forming macromolecule as organic perforating agent (cellulose/polyimides mass ratio 1:2) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by hydroxyapatite（HA）Powder and particle diameter distribution are pressed in 300 ~ 500 microns of inorganic perforating agent sodium acid carbonate
Volume ratio 2:1 is added in solution, is stirred by ultrasonic, and is uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous HA pottery
Porcelain.
Embodiment 9
Porous calcium phosphate ceramic is prepared according to the following steps：
A, prepared by solution：
A1, configuration volume ratio 1:2 acetone-ethanol mixed solution；
A2, using film forming macromolecule as organic perforating agent (cellulose/polyimides mass ratio 1:2) it is added to solution
In, the solution of 0.5g/ml is configured, is stirred by ultrasonic and is uniformly mixed；
A3, by calcium dihydrogen phosphate（DCPD）The inorganic perforating agent ammonium hydrogen carbonate of powder and particle diameter distribution at 300 ~ 500 microns
Example 1 by volume:2 are added in solution, are stirred by ultrasonic, and are uniformly mixed.
B, it is molded
A3 resulting solutions are placed into 15ml small beakers, -10 DEG C stand volatilization.Organic solvent is obtained after 5 days to be evaporated completely
Block materials after complete.
C, drilling
By the block materials obtained by B be put into boiling water 5 it is small when, remove inorganic perforating agent.
D, high temperature sintering
By sample obtained by C, 1100 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous calcium phosphate
Calcium dihydrogen ceramics.
The porous calcium phosphate of scanning electron microscope and omnipotent mechanics machine to gained in the various embodiments described above is respectively adopted
Calcium ceramics are characterized, the results show：The compression strength of porous calcium phosphate ceramic obtained by each embodiment is all not less than 4MPa, all
Multistage intercommunicating pore structure with macropore set aperture, and its porosity and pore size can be by adjusting the particle diameters of calcium phosphate powder
The parameters such as the additional proportion of distribution, calcium phosphate powder and pore-foaming agent are adjusted flexibly and are accurately controlled.Fig. 1-3 is respectively to implement
Stereoscan photograph of the porous HA ceramics under three kinds of different amplifications described in example 1, the as seen from the figure porous HA
Contain 100 ~ 500 microns abundant of macropore in ceramics, be interconnected between macropore by aperture, contain what is enriched on big hole wall
Micropore（< 20μm）.
Embodiment 10
In above-mentioned any embodiment, the mixed solution in step A1 is changed at least one of into acetone, chloroform, ethanol,
Change organic perforating agent in step A2 at least one of into polylactic acid, chitosan, cellulose, polyimides, polystyrene,
Change the inorganic perforating agent in step A3 at least one of into ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, can successfully prepare more
Hole calcium phosphate ceramic, the porous calcium phosphate ceramic of gained all have the multistage intercommunicating pore structure of macropore set aperture, porosity and hole
Footpath size is controllable, and compression strength is not less than 4MPa.Comparing result is shown：In the case where other conditions are identical, acetone, chlorine are selected
At least two mixed solution is more advantageous to the high molecular dissolving of film forming in imitative, ethanol, and is conducive to have in volatilization process
The film forming fixation of machine perforating agent forms base substrate；In the case where other conditions are identical, select polylactic acid/polystyrene mixture or
The mixture of cellulose/polyimides is more advantageous to film forming and fixes；In the case where other conditions are identical, ammonium hydrogen carbonate is selected to do
Inorganic perforating agent is better, its thermal decomposition product is all discharged as gas, in the product any residual of thing.
Embodiment 11
By cellulose and polyimides in mass ratio 1:2 ratio mixed dissolution is in the mixed of volatile solvent acetone and ethanol
Bonding solvent（Volume ratio 1:2）In be configured to the solution of 0.5 g/ml, it is 1 then to add volume ratio:1 calcium phosphate powder and carbonic acid
Hydrogen potassium mixes, and volatilization is stood at -15 DEG C removes solvent and obtain block materials, when block materials are put into immersion 2 is small in boiling water, goes
Except inorganic perforating agent, then sinter porcelain into and remove residual mineral perforating agent and organic perforating agent in sintering process at the same time, obtain
Porous calcium phosphate ceramic.
The pore structure of gained ceramics and mechanical property are similar to the HA porous ceramics of gained in the present embodiment, gained it is more
Hole calcium phosphate ceramic all has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable, and compression strength is not
Less than 4MPa.
Embodiment 12
Dissolve the chitosan in volatile solvent ethanol and be configured to the solution of 0.1 g/ml, then adding volume ratio is
0.8:1 calcium phosphate powder and sodium acid carbonate mixes, and volatilization removing solvent is stood at -5 DEG C and obtains block materials, by block materials
Be put into boiling water immersion 10 it is small when, remove inorganic perforating agent, then sinter porcelain into while residual mineral is removed in sintering process
Perforating agent and organic perforating agent, obtain porous calcium phosphate ceramic.
The pore structure of gained ceramics and mechanical property are similar to the HA porous ceramics of gained in the present embodiment, gained it is more
Hole calcium phosphate ceramic all has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable, and compression strength is not
Less than 4MPa.
Embodiment 13
By cellulose and polyimides in mass ratio 2:1 ratio mixed dissolution is in the mixed of volatile solvent chloroform and ethanol
Bonding solvent（Volume ratio 2:1）In be configured to the solution of 0.4 g/ml, it is 1 then to add volume ratio:2 calcium phosphate powder and carbonic acid
Hydrogen ammonium mixes, and volatilization is stood at -20 DEG C removes solvent and obtain block materials, when block materials are put into immersion 7 is small in boiling water, goes
Except inorganic perforating agent, then sinter porcelain into and remove residual mineral perforating agent and organic perforating agent in sintering process at the same time, obtain
Porous calcium phosphate ceramic.
The pore structure of gained ceramics and mechanical property are similar to the HA porous ceramics of gained in the present embodiment, gained it is more
Hole calcium phosphate ceramic all has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable, and compression strength is not
Less than 4MPa.
Embodiment 14 is co-cultured with cell
The porous calcium phosphate ceramic block prepared in above-mentioned any embodiment is taken, it is more for F12*2mm disc-shapeds to cut into size
Hole stent, is placed in soaked overnight in 75% alcohol, the PBS solution cleaning of sterilizing is placed on 24 well culture plates by the porous support
In, by every sheet material 2 × 104The inoculum density of a cell is by Bone Marrow Mesenchymal Stem Cells of Mice（MSCs）Cell inoculation is in porous branch
On frame material, 37 DEG C/5%CO is placed in2Cell culture is carried out in cell incubator；3 days poststainings of cell culture, are total to by laser
Focusing microscope（CLSM）Growing states of the MSCs on POROUS TITANIUM surface is observed, the results show cell is attached in material surface to be grown
Well, show that the porous titanium material has good biocompatibility.
Claims (6)
1. a kind of preparation method of porous calcium phosphate ceramic, it is characterised in that using film forming macromolecule as organic perforating agent
Coordinate water-soluble inorganic perforating agent, porous calcium phosphate ceramic is obtained by multistage drill process, it is specially that the film forming is high
Then molecular melting adds calcium phosphate powder and water-soluble inorganic perforating agent mixes, stand volatilization and remove in volatile solvent
Solvent obtains block materials, and block materials are put into boiling water, removes inorganic perforating agent, then sinters porcelain at the same time sintered
Residual mineral perforating agent and organic perforating agent are removed in journey, obtains porous calcium phosphate ceramic；The film forming macromolecule, which is used as, to be had
On the one hand machine perforating agent using its film forming characteristics is conducive to that calcium phosphate powder and inorganic perforating agent are fixed and be molded, another
Aspect, organic perforating agent after film forming form the organic backbone being mutually communicated of ceramic body, play that support is fixed to be made to base substrate
With, while the pore structure being mutually communicated can be left in ceramics after organic perforating agent is removed at high temperature；It is described into
Film macromolecule is polylactic acid, chitosan, cellulose, polyimides, at least one of polystyrene, the inorganic perforating agent
For at least one of ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate；The volatile solvent is acetone, at least two in chloroform, ethanol
The mixed solution of kind.
2. the preparation method of the porous calcium phosphate ceramic according to claim 1, it is characterised in that the porous calcium phosphate
Ceramics have self-bone grafting and osteoconductive nature.
3. the preparation method of porous calcium phosphate ceramic according to claim 1, it is characterised in that the calcium phosphate is phosphorus
At least one of sour tricalcium, hydroxyapatite, tetracalcium phosphate, calcium dihydrogen phosphate.
4. the preparation method of porous calcium phosphate ceramic according to claim 1, it is characterised in that sintering temperature for 800~
1300℃。
5. the preparation method of porous calcium phosphate ceramic according to claim 1, it is characterised in that comprise the following steps that：
A, prepared by slurry：
A1, prepare volatile solvent：Any two kinds in acetone, chloroform, ethanol are taken, according to volume ratio 1：1 ratio mixing；
A2, using film forming macromolecule as organic perforating agent be added to A1 steps obtained by volatile solvent in, prepare 0.1~
The mixed solution of 0.5g/ml, ultrasonic agitation are uniformly mixed；
A3, by the inorganic perforating agent of calcium phosphate powder and certain particle diameter be proportionally added into obtained mixed solution in A2 steps
In, it is stirred by ultrasonic, is uniformly mixed；
B, it is molded
Slurry obtained by A3 is stood into volatilization at -20 ~ -5 DEG C, obtains the block materials after volatile solvent volatilization completely；
C, drilling
Block materials obtained by B are put into boiling water and are soaked, remove inorganic perforating agent；
D, high temperature sintering
By sample obtained by C, 800~1300 DEG C of high temperature sinterings remove residual mineral perforating agent and organic perforating agent, obtain porous phosphorus
Sour calcium ceramics.
6. the porous calcium phosphate ceramic prepared according to claim 1 the method, it is characterised in that the porous calcium phosphate pottery
Porcelain has the multistage intercommunicating pore structure of macropore set aperture, and porosity and pore size are controllable, and compression strength is not less than 4MPa.
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| CN108546107B (en) * | 2018-03-21 | 2021-05-28 | 山东大学深圳研究院 | Gradient porous calcium polyphosphate ceramic material and preparation method thereof |
| CN108793845A (en) * | 2018-07-05 | 2018-11-13 | 叶露穗 | A kind of calcium phosphate bioactive ceramics and preparation method thereof |
| CN113101410B (en) * | 2021-03-22 | 2022-05-24 | 华南理工大学 | Tricalcium phosphate support with uniform mesopore and three-dimensional communicated hierarchical pore structure as well as preparation method and application of tricalcium phosphate support |
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