CN102942358B - Preparation method of fluorinated hydroxyapatite (HA) composite material with uniform porous structure - Google Patents
Preparation method of fluorinated hydroxyapatite (HA) composite material with uniform porous structure Download PDFInfo
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- CN102942358B CN102942358B CN201210473676.3A CN201210473676A CN102942358B CN 102942358 B CN102942358 B CN 102942358B CN 201210473676 A CN201210473676 A CN 201210473676A CN 102942358 B CN102942358 B CN 102942358B
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- hydroxyapatite
- fluoridize
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Abstract
Disclosed is a preparation method of a fluorinated HA composite material with a uniform porous structure. The method includes taking ammonium bicarbonate and polymethyl methacrylate (PMMA) as foaming agents, subjecting the agents and fluorinated hydroxyapatite generated through a sol-gel method to a two-step foaming method, and finally obtaining the fluorinated hydroxyapatite composite material with the nanoscale porous structure. According to the method, the pore structure with uniform size and mutually communicated pores is obtained through control of implementation conditions, when the material is transplanted into a human body, cells can grow in the pores so as to form tight combination with human body tissues, and the stability of the material is strengthened during a fluorination process. The porous structure can provide pore channels and grow space for fiber cells and osseous tissues to grow into the material, the contact surface area of interstitial fluid with the HA is increased, and the normal metabolism relationship of the human body can be maintained.
Description
Technical field
What the present invention relates to is a kind of material and method of technical field of nano material, specifically a kind of infiltration of applicable osseous tissue growth, have uniformly interconnect, the preparation method who fluoridizes hydroxyapatite composite material of the vesicular structure of size between 100-300 micron.
Background technology
Hydroxyapatite (Hydroxyapatite, HA) is the basic inorganic components of skeleton, has good biocompatibility and biological activity.Hydroxyapatite has become biological restoration and the equivalent material that human body hard tissue is good, and studying novel and hydroxyapatite premium properties has also become study hotspot.But simple hydroxyapatite less stable, fluoridizes hydroxyapatite by implementation method, generate and fluoridize hydroxyapatite, strengthen the stability of hydroxyapatite.But for the replacement of general human bone, need to form bone structure and support people's body, this just needs just to play a role with the compact biological substitution material of human body soft tissue.The synthetic biological substitution material with porous composite structure becomes the emphasis of research.
Through the retrieval of prior art is found, Wang Song congruence has been recorded in " porous ceramics and performance study thereof are prepared in the compound pore-creating of bicarbonate of ammonia and polyvinyl alcohol ": taking hydroxyapatite (HA) as matrix, adopt the method for adding NH4HCO3 crystal grain and adding heat abstraction to prepare porous hydroxyapatite (HA) pottery, in preparation process, add a certain amount of bio-vitric to increase its intensity simultaneously, add a certain amount of polyvinyl alcohol (PVA) and improve its bonding properties and improve connectivity.Porous bio-ceramic sample to preparation carries out hardness and compressive strength test, and the affect rule of different components on its performance is discussed, and adopts the microstructure analysis of scanning electron microscope to porous ceramics sample.Result shows, along with the increase of NH4HCO3 content, the porosity of porous bio-ceramic sample and hardness increase, and ultimate compression strength declines, and aperture is about 200-300 μ m; Along with the increase of PVA content, sample porosity increases, and connectivity strengthens, and orifice throat length is about 1～3mm, and aperture is below 100 μ m; Along with the increase of bio-vitric content, the volumetric shrinkage of sample is obvious, micropore increases, but this technology is taking NH4HCO3 as main pore-forming material, NH4HCO3 just decomposes than being easier at low temperatures, thus in this technology sample in sintering process, when low temperature, most NH4HCO3 decomposes generation bubble very soon, make the pore of generation inhomogeneous, and sample is produced to certain stress, the porous heterogeneity that the ununiformity of gas also makes sample produce.
Chinese patent literature CN1903706, open day 20070131, record a kind of " preparation method of hydroxyapatite tiny balloon ", the method is taking four water-calcium nitrate and Secondary ammonium phosphate as raw material, adopt the chemical precipitation method in wet method, prepare hydroxyapatite slip; Then with distilled water, hydroxyapatite slip is diluted, and add the bicarbonate of ammonia as additive, after stirring, spray dry, in conjunction with subsequent heat treatment, the hydroxyapatite tiny balloon that obtains being formed by nanocrystal.The product that utilizes the inventive method gained, microballoon is made up of nanocrystal, and powder size is little, epigranular, specific surface area is large, and hollow rate is high, and degree of crystallinity is lower; Not only there is excellent biocompatibility, good sphericity; And whole preparation method's process is simple, cost is lower.The prepared hydroxyapatite tiny balloon of the present invention, is expected to be applied in fields such as injection type slow releasing carrier of medication, the damaged weighting material of bone and separation and purifications.But during this technology can not be applied to the bulk reparation of human bone and replaces, and evenly connected vesicular structure be human cell tissue growth passage and space be provided.
Summary of the invention
The present invention is directed to prior art above shortcomings, propose a kind of preparation method who there is even vesicular structure and fluoridize hydroxyapatite composite material, adopted two step foamings, NH
4hCO
3be not main whipping agent, and in the foaming of the slow baking stage of low temperature, the pore of generation is comparatively even, the follow-up macromolecular sustained slow vaporization stage can be evenly connected porous; By fluoridizing hydroxyapatite and PMMA(polymethylmethacrylate) complex sintered become a kind of vesicular structure, by controlling implementation condition, obtain size homogeneous, the pore structure being interconnected, when being transplanted in human body, can make cell grow in hole, form combination closely with this and tissue.And through fluorination process, strengthen the stability of material.Vesicular structure can be grown wherein duct and growing space are provided for fibrocyte and osseous tissue, and augmenting tissue liquid and hydroxyapatite contact surface area keep the metabolism relation of human normal.
The present invention is achieved by the following technical solutions, the present invention adopts bicarbonate of ammonia and polymethylmethacrylate (PMMA) as whipping agent, carry out two step foamings with the hydroxyapatite of fluoridizing generating by sol-gel method, finally obtain having the hydroxyapatite composite material of fluoridizing of nanometer porous structure.
Described method concrete steps comprise:
The first step, generate and fluoridize hydroxyapatite Ca by sol-gel method
10(PO
4)
6(OH)
2-2xf
2x0.5g polymethylmethacrylate (PMMA), 1g sodium lauryl sulphate (SDS) and 0.8g are fluoridized to three kinds of powder of hydroxyapatite and be placed in the mould that 25mL, diameter be about 3cm and be fully uniformly mixed, fluoridize hydroxyapatite and PMMA is thoroughly mixed to form uniform pore structure to allow; Taking PMMA as main foaming agent, form micron order hole, add tensio-active agent, fully connect organic phase and inorganic phase, powder is mixed more abundant.
By implementing to prove that, in the time that x is greater than 0.5, sample thermostability strengthens early stage, in the time that generating porous material, reduces high temperature sintering the thermolysis effect of phosphatic rock, and therefore preferred fluorinated hydroxyapatite is Ca
10(PO
4)
6(OH)
0.8f
1.2, Ca
10(PO
4)
6(OH)
0.6f
1.4or Ca
10(PO
4)
6(OH)
0.4f
1.6.
Described sol-gel method refers to:
I) ca nitrate soln, Secondary ammonium phosphate are made into respectively to the homogeneous solution of 0.2mol/L with pure water, with ammoniacal liquor be 11 by the pH regulator of solution respectively;
Ii) Neutral ammonium fluoride is made into the uniform solution that concentration is 0.2mL/L with pure water, regulating pH value with ammoniacal liquor is 11.
Iii) first ammonium dibasic phosphate solution is added dropwise in ca nitrate soln and generates hydroxyapatite with the speed of 0.5mL/s, add ammonium fluoride solution to generate with identical speed afterwards and fluoridize hydroxyapatite; In reaction process, constantly stirring and regulating pH regulator is 11, and whipping process continues 5h.
Iv) by the ageing of solution 24 hours generating, outwell supernatant liquor, ultrasonic to colloidal sol, centrifugal, washing, in triplicate, carries out sintering realization after drying afterwards at 80 DEG C of temperature in the temperature range of 600 DEG C-1120 DEG C.
Aforesaid method is reacted and can be obtained Ca by the ammonium fluoride solution of configuration different concns
10(PO
4)
6(OH)
0.8f
1.2, Ca
10(PO
4)
6(OH)
0.6f
1.4or Ca
10(PO
4)
6(OH)
0.4f
1.6.
Second step, by 0.2 bicarbonate of ammonia fully dissolve in 1.5mL pure water, form homogeneous solution and with the mould being added dropwise in the first step in, and use glass stick uniform stirring, form uniform colloidal sol; The object of doing is like this to make the foaming process of bicarbonate of ammonia more even, the bicarbonate of ammonia being uniformly dissolved completely can not produce suddenly a large amount of gas, produce uniformly micropore, and mixed uniformly PMMA volatilization uniformly in sintering process has formed uniform vesicular structure, is applicable to the infiltration growth of osseous tissue.
The 3rd step, colloidal sol is placed in air to moisture evaporation and forms and approach solid-state gel, afterwards gel is placed in baking oven, at 70 DEG C of temperature, place 5h, until dry, by the bubble of bicarbonate of ammonia decomposition generation, material is formed and there is sandwich micropore, inner connected.
The 4th step, the sample of oven dry is placed on and in melting furnace, carries out sintering, with the rate of heating heating of 10 DEG C/min, control rate of heating, make PMMA evenly volatilize slowly to avoid cracking, make temperature rise to 600 DEG C, and keep 0.5h, form the vesicular structure interconnecting.And crack avoiding so that identical speed is cooling.
What the present invention prepared by aforesaid method fluoridizes hydroxyapatite composite material, there is the pore space structure that applicable human body cell infiltrates growth and the interconnective homogeneous of bone, the size of hole is between 100-300 micron, and between material internal, form the interconnective internal structure of hole, can strengthen the infiltration of cell tissue growth and tissue juice, make more compact and firm of tissue growth, promote the reparation of bone.
What the present invention prepared by aforesaid method fluoridizes hydroxyapatite composite material, can be used for preparing the block repair materials of body bone tissue.
The present invention has not only generated the highly purified hydroxyapatite of fluoridizing, and has strengthened thermostability, has produced vesicular structure again in the foaming sintering stage, for the application of the block repair materials of body bone tissue provides good reference.
Brief description of the drawings
Fig. 1 is the SEM scintigram that embodiment 2 porous are fluoridized hydroxyapatite composite material.
As can be seen, by 0.8g Ca
10(PO
4)
6(OH)
0.4f
1.6, 0.5g polymethylmethacrylate, three kinds of powder of 1g sodium lauryl sulphate fully mix obtained sample.0.2g bicarbonate of ammonia is dissolved in the pure water of 1.5mL, injects afterwards mixed powder, stir and dry sintering, the size in hole is between 100-300 micron.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented under taking technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
What use is the hydroxyapatite of fluoridizing generating with sol-gel method, more composite porous with polymethylmethacrylate composition generation, specifically implements characterizing method as follows.
0) prepare Ca
10(PO
4)
6(OH)
0.8f
1.2:
I) ca nitrate soln, Secondary ammonium phosphate are made into respectively to the homogeneous solution of 0.2mol/L with pure water, with ammoniacal liquor be 11 by the pH regulator of solution respectively;
Ii) Neutral ammonium fluoride is made into the uniform solution that concentration is 0.2ml/L with pure water, regulating pH value with ammoniacal liquor is 11.
Iii) first ammonium dibasic phosphate solution is added dropwise in ca nitrate soln and generates hydroxyapatite with the speed of 0.5mL/s, add ammonium fluoride solution to generate with identical speed afterwards and fluoridize hydroxyapatite; In reaction process, constantly stirring and regulating pH regulator is 11, and whipping process continues 5h.
Iv) by the ageing of solution 24 hours generating, outwell supernatant liquor, ultrasonic to colloidal sol, centrifugal, washing in triplicate, is carried out sintering after drying afterwards and obtain Ca at 80 DEG C of temperature in the temperature range of 600 DEG C-1120 DEG C
10(PO
4)
6(OH)
0.8f
1.2.
1) by 0.8g Ca
10(PO
4)
6(OH)
0.8f
1.2, 0.3g polymethylmethacrylate, three kinds of powder of 1g sodium lauryl sulphate be placed in small beaker and stir, and it is fully mixed.The vesicular structure that allows PMMA produce is more even.
2) 0.1g bicarbonate of ammonia is dissolved in the pure water of 1.5mL, constantly concussion is dissolved it completely; After being first uniformly dissolved, mix with powder, foaming process is more even again, also homogeneous of the micropore of generation.
3) will obtain gel and dry at 70 DEG C of temperature, in surface and the inner pore structure that has formed uniform nano-scale of material.
4) by material sintering in melting furnace of drying, be heated to 600 DEG C of degree with the speed of 10 DEG C/min, control rate of heating, and keep 0.5h at 600 DEG C of temperature, obtain uniform interconnective vesicular structure.
By the pattern of surface sweeping electron microscope observation product, the present embodiment preparation has formed has uniform interconnective vesicular structure, the size in hole between 100-150 micron, the porosity of sample.
Embodiment 2
What use is the hydroxyapatite of fluoridizing generating with sol-gel method, more composite porous with polymethylmethacrylate composition generation, specifically implements characterizing method as follows.
1) by 0.8g Ca
10(PO
4)
6(OH)
0.6f
1.4, 0.5g polymethylmethacrylate, three kinds of powder of 1g sodium lauryl sulphate be placed in small beaker and stir, and it is fully mixed.The vesicular structure that allows PMMA produce is more even.
2) 0.2g bicarbonate of ammonia is dissolved in the pure water of 1.5mL, constantly concussion is dissolved it completely; After being first uniformly dissolved, mix with powder, foaming process is more even again, also homogeneous of the micropore of generation.
3) will obtain gel and dry at 70 DEG C of temperature, in surface and the inner pore structure that has formed uniform nano-scale of material.
4) by material sintering in melting furnace of drying, be heated to 600 DEG C of degree with the speed of 10 DEG C/min, control rate of heating, and keep 0.5h at 600 DEG C of temperature, obtain uniform interconnective vesicular structure.
By the pattern of surface sweeping electron microscope observation product, as shown in Figure 1, the present embodiment has formed has uniform interconnective vesicular structure, and the size in hole is between 100-300 micron, and sample porosity is moderate.
Embodiment 3
What use is the hydroxyapatite of fluoridizing generating with sol-gel method, more composite porous with polymethylmethacrylate composition generation, specifically implements characterizing method as follows.
1) by 0.8g Ca
10(PO
4)
6(OH)
0.4f
1.6, 0.8g polymethylmethacrylate, three kinds of powder of 1g sodium lauryl sulphate be placed in small beaker and stir, and it is fully mixed.The vesicular structure that allows PMMA produce is more even.
2) 0.3g bicarbonate of ammonia is dissolved in the pure water of 1.5mL, constantly concussion is dissolved it completely; After being first uniformly dissolved, mix with powder, foaming process is more even again, also homogeneous of the micropore of generation.
3) will obtain gel and dry at 70 DEG C of temperature, in surface and the inner pore structure that has formed uniform nano-scale of material.
4) by material sintering in melting furnace of drying, be heated to 600 DEG C of degree with the speed of 10 DEG C/min, control rate of heating, and keep 0.5h at 600 DEG C of temperature, obtain uniform interconnective vesicular structure.
By the pattern of surface sweeping electron microscope observation product, the present embodiment preparation has formed has uniform interconnective vesicular structure, and the size in hole is between 200-400 micron, and the porosity of sample is bigger.
Claims (4)
1. a preparation method who there is even vesicular structure and fluoridize hydroxyapatite composite material, it is characterized in that, adopt bicarbonate of ammonia and polymethylmethacrylate as whipping agent, generate the hydroxyapatite composite material of fluoridizing with nanometer porous structure by sol-gel method; Described method concrete steps comprise:
The first step, generate and fluoridize hydroxyapatite Ca by sol-gel method
10(PO
4)
6(OH)
2-2xf
2x, by polymethylmethacrylate, sodium lauryl sulphate with fluoridize three kinds of powder of hydroxyapatite and be placed in mould and be fully uniformly mixed, fluoridize hydroxyapatite and PMMA is thoroughly mixed to form uniform pore structure to allow;
Second step, bicarbonate of ammonia is fully dissolved in and in pure water, forms homogeneous solution and be added dropwise in the mould in the first step, and use glass stick uniform stirring, form uniform colloidal sol;
The 3rd step, colloidal sol is placed in air to moisture evaporation and forms and approach solid-state gel, afterwards gel is placed in baking oven and is dried, by bicarbonate of ammonia decompose the bubble generating material is formed have micropore, the connected sandwich in inside.
The 4th step, the sample of oven dry is placed on and in melting furnace, carries out sintering, with the rate of heating heating of 10 DEG C/min, control rate of heating, make PMMA evenly volatilization slowly do not crack; Treat that temperature rise to 600 DEG C keeps 0.5h, form the vesicular structure interconnecting, last with identical speed cooling down to avoid producing tiny crack;
Described generate and fluoridize hydroxyapatite and refer to by sol-gel method:
I) ca nitrate soln, Secondary ammonium phosphate are made into respectively to the homogeneous solution of 0.2mol/L with pure water, with ammoniacal liquor be 11 by the pH regulator of solution respectively;
Ii) Neutral ammonium fluoride is made into the uniform solution that concentration is 0.2mL/L with pure water, regulating pH value with ammoniacal liquor is 11;
Iii) first ammonium dibasic phosphate solution is added dropwise in ca nitrate soln and generates hydroxyapatite with the speed of 0.5mL/s, add ammonium fluoride solution to generate with identical speed afterwards and fluoridize hydroxyapatite; In reaction process, constantly stirring and regulating pH value is 11, and whipping process continues 5h;
Iv) by the ageing of solution 24 hours generating, outwell supernatant liquor, ultrasonic to colloidal sol, centrifugal, washing, in triplicate, carries out sintering realization after drying afterwards at 80 DEG C of temperature in the temperature range of 600 DEG C-1120 DEG C.
2. method according to claim 1, is characterized in that, the described hydroxyapatite of fluoridizing is Ca
10(PO
4)
6(OH)
0.8f
1.2, Ca
10(PO
4)
6(OH)
0.6f
1.4or Ca
10(PO
4)
6(OH)
0.4f
1.6.
One kind prepare according to method described in above-mentioned arbitrary claim fluoridize hydroxyapatite composite material, it is characterized in that, there is the pore space structure that applicable human body cell infiltrates growth and the interconnective homogeneous of bone, the size of hole, between 100-300 micron, and has formed the interconnective internal structure of hole between material internal.
4. application of fluoridizing hydroxyapatite composite material according to claim 3, is characterized in that, for the preparation of the block repair materials of body bone tissue.
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| CN103170006A (en) * | 2013-04-12 | 2013-06-26 | 上海交通大学 | Method for preparing porous hydroxyapatite scaffold via two-step process |
| CN103341213B (en) * | 2013-06-25 | 2015-06-24 | 上海交通大学 | Preparation method for FHA/beta-TCP (fluorhydroxyapatite/beta-tertiary calcium phosphate) diphasic fluoridated hydroxyapatite 3D (three-dimensional) porous scaffold |
| CN105439626B (en) * | 2015-11-30 | 2018-04-24 | 四川大学 | A kind of preparation method of porous calcium phosphate ceramic |
| CN105920673B (en) * | 2016-05-18 | 2019-03-05 | 上海交通大学 | Complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient |
| CN106045495B (en) * | 2016-05-25 | 2018-07-03 | 西南科技大学 | A kind of porous fluor-apatite ceramic preparation of Adsorption of Radioactive nucleic |
| CN108324987B (en) * | 2018-02-09 | 2020-11-24 | 华南理工大学 | Hollow porous spherical particle artificial bone and preparation method and application thereof |
| CN108355401B (en) * | 2018-02-09 | 2021-01-08 | 纳琦环保科技有限公司 | Preparation method of inorganic porous purification filter element |
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| CN102229494B (en) * | 2011-06-03 | 2013-06-12 | 东北大学 | Preparation method for macroporous hydroxyapatite ceramic |
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