CN103086339A - Porous hydroxyapatite flower-like microspheres and preparation method thereof - Google Patents
Porous hydroxyapatite flower-like microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention discloses porous hydroxyapatite flower-like microspheres and a preparation method thereof. The preparation method comprises the following steps: adding 80 DEG C distilled water into CaO to slake the CaO into 1-10 wt% Ca(OH)2 slurry, introducing a CO2/N2 gas mixture into the slurry at room temperature while mechanically stirring, and stopping the reaction when the pH value of the reaction system reaches 7; under the conditions of heating and stirring, adding Al(OH)3 and a phosphate solution, wherein an NaOH solution is added in the reaction process to keep the pH value of the reaction system at 10.0; after some time, centrifuging, and washing the precipitate until the pH value of the solution is approximate to a neutral state; and centrifuging, and drying to obtain the porous hydroxyapatite flower-like microsphere powder product. The invention does not need to add any complex organic substance, polymer or the like, and also does not need to add any operation step for removing the template after the reaction; meanwhile, no impurity appears in the product, and thus, the method is simple to operate and low in cost, thereby laying foundation for industrial production; and the prepared porous hydroxyapatite flower-like microspheres have huge application prospects in the fields of tissue engineering, drug delivery and the like.
Description
Technical field
The present invention relates to flower-shaped microballoon of a kind of porous hydroxyapatite and preparation method thereof, belong to the preparation field of inorganic materials.
Background technology
At present according to pore-creating (or pore-forming) principle, porous hydroxyapatite (Ca
10(PO
4)
6(OH)
2, preparation method HAP) can be divided into biomimetic method (Dominic Walsh, Chem Mater, 1996,8,1994-2001; Mao Chuanbin, chemical progress, 1998,9,246-254), sintering process (H, USPatent, 1987-06-17), the pore-forming material method, the whipping agent method, template (Hing K A, J Mater Sci:Mater in Medicine, 1999,10,135-145), the seven large classes such as three-dimensional design rapid shaping technique.At present the research institution of the overwhelming majority all is devoted to through making pore-forming material burning or decomposition removal after calcining, finally to make Porous HAP by HAP powder and pore-forming material etc. are mixed.(Arita I H, Biomaterials, 1995,16, the 403-408 such as Ryshkewitch; E, J Am Ceram Soc, 1953,36,65-68; Klein C, Biomaterials, 1994,15,31-34) utilize the decomposing gas legal system for Porous HAP.Liu (Dean-Mo, Biomaterials, 1996,17,1955-1957) use polyvinyl butyral acetal (PVB) further to control the pore texture of Porous HAP as the particle diameter of pore-forming material and control PVB.(Yao Xiumin, functional materials and device journal, 2000,6, the 153-156 such as Yao Xiumin; Yao Xiumin, Journal of Inorganic Materials, 2000,3,467-472) use respectively polymethylmethacrylate (PMMA), the inorganics carbon dust finally makes Porous HAP as pore-forming material.Use the precast body method of forming (Hassna RR, Biomaterials, 2003,24,3293-3302; Pierre L, J Am Ceram Soc, 1998,81,1421-1428; Tancred D C, Biomaterials, 1998,19,2303-2311; Yang X, J Mater Chem, 1998,8,2233-2237; Zhao Junliang, Chinese pottery, 2003,39,4-7), at first make the open precast body of hole, then it is mixed with hydroxyapatite, thereby remove precast body formation Porous HAP through oversintering or other approach.The whipping agent method is exactly with hydrogen peroxide, take water-soluble polymerss such as polyvinyl alcohol as binding agent, and perhaps also can be with polyvinyl butyral acetal or methylcellulose gum (Engin N O, J Europ Ceram Soc, 1999,19,2569-2572) prepare Porous HAP as whipping agent.The template synthetic technology is the effective means of the orderly porous material of preparation, is a kind of method of biosimulation synthetic materials.Be mainly with the inorganics precursor under the effect of template, by the interface interaction of organic supermolecular/inorganics, form and to have the inorganic materials of a fixed structure and pattern.Sometimes, also need to add catalyzer or auxiliary agent (as cosolvent etc.).Its forming process mainly contains hydro-thermal or solvent thermal synthesis method and acid room temperature synthesis method, and sol-gel method.Then desolventizing is removed template through calcining or chemical treatment, obtains porous material (He Q J, Mater Lett, 2007,61,141-143; Qin Zhenping, the chemical industry progress, 2002,21,323-327).The three-dimensional design rapid shaping technique still is in the development phase at present, and the time that also needs to grow could really be applied to organizational project.No matter be to adopt which kind of method, the reactions steps that all needs to add organism and complexity just can be prepared porous hydroxyapatite.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides flower-shaped microballoon of a kind of simple porous hydroxyapatite and preparation method thereof.
Technical scheme: for achieving the above object, the preparation method of the flower-shaped microballoon of porous hydroxyapatite of the present invention comprises the following steps:
(1) CaO being added 80 ° of C distilled water be digested to mass concentration is 1%～10% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully more than 10h; Under room temperature, and pass into CO to slurries in mechanical stirring
2/ N
2Mixed gas (CO
2And N
2Mol ratio is 0.1～0.5, and speed is 1L/min, and pH value of reaction system reaches 7 o'clock stopped reaction; Then add Al (OH)
3Solution, the mol ratio of calcium and aluminium is at 5:1～50:1;
Add phosphate solution under (2) 60 ° of C agitation conditions, reaction is centrifugal after 2～4h, washing precipitation is until pH reaches 7, obtains the flower-shaped microballoon powder-product of porous hydroxyapatite after centrifugal, drying.
What wherein, described phosphoric acid salt can be in Sodium phosphate dibasic, sodium phosphate is a kind of.
Agitation condition in described step (1) and step (2) is 200～600 rev/mins.
In described step (2), adding NaOH solution to keep reacting system PH value in reaction process is 10.0.
The flower-shaped microballoon of porous hydroxyapatite that adopts aforesaid method to prepare, its microballoon all is spheroidal, and is rough, and median size is 2-4 μ m, and is dispersed fine; Each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, and lamellar spacing 20～30nm, the diameter of the hole of composition are 200～300nm.
Beneficial effect: compared with prior art, the preparation method of the flower-shaped microballoon of porous hydroxyapatite of the present invention has the following advantages:
1, the present invention does not need to add complicated organism, polymkeric substance etc., and also do not need to increase operation steps because remove template after reaction;
2, the present invention does not have impurity to occur in product, and both simple to operate, with low cost again, for its suitability for industrialized production is laid a good foundation, the flower-shaped microballoon of the porous hydroxyapatite of preparation has huge application prospect in fields such as organizational project, drug delivery;
3, the pattern of product has not only been controlled in the interpolation of aluminium hydroxide in the present invention in reaction, and has promoted the hydroxyapatite crystal growth, has greatly shortened the reaction times.
The flower-shaped microballoon of the porous hydroxyapatite that adopts preparation method of the present invention to make has the following advantages:
1, the flower-shaped microballoon of this hydroxyapatite all is spheroidal, and median size is 2～4 μ m approximately, and is dispersed fine; Each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, and lamellar spacing 20～30nm, the diameter of the hole of composition are 200～300nm; This structure can improve the specific surface area of product greatly, spherical product is played the effect of enhancing in application facet such as separation and absorption;
2, the main crystal face diffraction peak of the flower-shaped microballoon of this hydroxyapatite is consistent with the crystal face diffraction peak of hydroxyapatite, and the diffraction peak of the product of preparation is very strong, and the degree of crystallinity of interpret sample is fine, is conducive to its application aspect chromatographic separation;
3, the flower-shaped microballoon of porous hydroxyapatite does not decompose after 800 ° of C roasting 6h, is still the crystalline structure of hydroxyapatite, illustrates that it has very high thermostability.
Description of drawings
The stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that Fig. 1 the present invention makes under the processing condition of embodiment 1; Wherein, Fig. 1 a is the low power stereoscan photograph, and Fig. 1 b is the high power stereoscan photograph;
The X-ray diffractogram of the flower-shaped microballoon of porous hydroxyapatite that Fig. 2 the present invention makes under the processing condition of embodiment 1;
The EDX spectrum of the flower-shaped microballoon of porous hydroxyapatite that Fig. 3 the present invention makes under the processing condition of embodiment 1;
The stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that Fig. 4 the present invention makes under the processing condition of embodiment 2;
The stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that Fig. 5 the present invention makes under the processing condition of embodiment 3;
The stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that Fig. 6 the present invention makes under the processing condition of embodiment 4.
Embodiment
The preparation method of the flower-shaped microballoon of a kind of porous hydroxyapatite of the present invention comprises the steps:
At first CaO being added 80 ° of C distilled water to be digested to concentration is 1%～10% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully more than 10h; At room temperature in mechanical stirring to Ca (OH)
2Slurries pass into CO
2/ N
2Mixed gas, CO
2And N
2Mol ratio is 0.1～0.5, and speed is 1L/min, and it is stopped reaction that pH value of reaction system reaches 7.
Then add Al (OH)
3, the mol ratio of calcium and aluminium is at 5:1～50:1; Add phosphate solution under heating (normally 60 ℃) agitation condition, adding NaOH solution to keep reaction system PH in reaction process is 10.0, after reaction 2～4h, white precipitate is separated from mother liquor, and with distilled water centrifugation washing precipitation until pH approach neutral or reach neutral, be the pH value near 7 or reach 7, obtain the flower-shaped microballoon powder-product of porous hydroxyapatite after centrifugal, drying.
Wherein, phosphoric acid salt is a kind of in Sodium phosphate dibasic, sodium phosphate; Agitation condition in step (1) and step (2) is 200～600 rev/mins.
The flower-shaped microballoon of the porous hydroxyapatite that aforesaid method prepares, it all is spheroidal, and median size is 2～4 μ m, and is dispersed fine; Each spherical surface is porous, and nanoparticle that these pore textures are sheet structure is assembled and to be formed, and lamellar spacing 20～30nm, the diameter of the hole of composition are 200～300nm.
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1:
Adding 80 ° of C distilled water to be digested to mass concentration 0.56g CaO is 1% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully at 11h.Under room temperature, and pass into CO to slurries in mechanical stirring
2/ N
2Mixed gas (CO
2And N
2Mol ratio is 0.2), speed is 1L/min, pH value of reaction system reaches 7 stopped reaction.Add again Al (OH)
3, the mol ratio of calcium and aluminium is 20:1.Electric stirring under 60 ° of C water-baths, with the 0.3mol/L sodium radio-phosphate,P-32 solution dropping 20ml of preparation, adding NaOH solution to keep reaction system PH in reaction process is 10.0, reaction 2h.Centrifugal, washing precipitation is until pH reaches 7, and is centrifugal, at the dry 24h of 80 ° of C, obtains powder-product.Agitation condition in the present embodiment is 200 rev/mins.
Adopt the flower-shaped microballoon of field emission microscopy observation hydroxyapatite, as shown in Figure 1, the pattern of hydroxyapatite particle all is spheroidal, and is rough, and median size is 4 μ m, dispersed fine, as shown in Figure 1a.Further observe and find, each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, and lamellar spacing 30nm, the diameter of the hole of composition are 300nm, as shown in Fig. 1 b.Fig. 2 is the X-ray diffractogram of the flower-shaped microballoon of porous hydroxyapatite that makes under this implementing process condition; Fig. 3 is the EDX spectrum of the flower-shaped microballoon of porous hydroxyapatite that makes under this implementing process condition.
Embodiment 2:
Adding 80 ° of C distilled water to be digested to mass concentration 0.56g CaO is 3% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully more than 12h.Under room temperature, and pass into CO to slurries in mechanical stirring
2/ N
2Mixed gas (CO
2And N
2Mol ratio is 0.3), speed is 1L/min, pH value of reaction system reaches 7 stopped reaction.Then add Al (OH)
3, the mol ratio of calcium and aluminium is 10:1.Electric stirring under 60 ° of C water-baths is with the 0.3mol/L Na of preparation
2HPO
4Solution drips 20ml, and adding NaOH solution to keep reaction system PH in reaction process is 10.0, reaction 3h.Centrifugal, washing precipitation is until pH reaches 7, and is centrifugal, obtains powder-product after the dry 24h of 80 ° of C.Agitation condition in the present embodiment is 300 rev/mins.
Fig. 4 is the stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that makes under this implementing process condition.The pattern of the flower-shaped microballoon of porous hydroxyapatite for preparing in the present embodiment all is spheroidal, rough, median size is 2 μ m, dispersed fine, further observe and find, each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, lamellar spacing 20nm, the diameter of the hole of composition are 200nm.
Embodiment 3:
Adding 80 ° of C distilled water to be digested to mass concentration 0.56g CaO is 10% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully at 15h.Under room temperature, and pass into CO to slurries in mechanical stirring
2/N
2Mixed gas (CO
2And N
2Mol ratio is 0.5), speed is 1L/min, pH value of reaction system reaches 7 stopped reaction.Then add Al (OH)
3, the mol ratio of calcium and aluminium is 5:1.Electric stirring under 60 ° of C water-baths, with the 0.3mol/L sodium radio-phosphate,P-32 solution dropping 20ml of preparation, adding NaOH solution to keep reaction system PH in reaction process is 10.0, reaction 4h.Centrifugal, washing precipitation is until pH reaches 7, and is centrifugal, obtains powder-product after the dry 24h of 80 ° of C.Agitation condition in the present embodiment is 400 rev/mins.
Fig. 5 is the stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that makes under this implementing process condition.
Embodiment 4:
Adding 80 ° of C distilled water to be digested to mass concentration 0.56g CaO is 5% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully at 18h.Under room temperature, and pass into CO to slurries in mechanical stirring
2/ N
2Mixed gas (CO
2And N
2Mol ratio is 3:10), speed is 1L/min, pH value of reaction system reaches 7 stopped reaction.Then add Al (OH)
3, the mol ratio of calcium and aluminium is 50:1.Electric stirring under 60 ° of C water-baths is with the 0.3mol/L Na of preparation
2HPO
4Solution drips 20ml, and adding NaOH solution to keep reaction system PH in reaction process is 10.0, reaction 2h.Centrifugal, washing precipitation obtains powder-product until pH approaches neutrally, centrifugal after the dry 24h of 80 ° of C.Agitation condition in the present embodiment is 500 rev/mins.
Fig. 6 is the stereoscan photograph of the flower-shaped microballoon of porous hydroxyapatite that makes under this implementing process condition.The pattern of the flower-shaped microballoon of porous hydroxyapatite for preparing in the present embodiment all is spheroidal, rough, median size is 3 μ m, dispersed fine, further observe and find, each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, lamellar spacing 25nm, the diameter of the hole of composition are 250nm.
Embodiment 5:
Adding 80 ° of C distilled water to be digested to mass concentration 0.56g CaO is 8% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully more than 10h.Under room temperature, and pass into CO to slurries in mechanical stirring
2/ N
2Mixed gas, CO
2And N
2Mol ratio is 0.1, and speed is 1L/min, and pH value of reaction system reaches 7 stopped reaction.Then add Al (OH)
3, the mol ratio of calcium and aluminium is 30:1.Electric stirring under 60 ° of C water-baths is with the 0.3mol/L Na of preparation
2HPO
4Solution drips 20ml, and adding NaOH solution to keep reaction system PH in reaction process is 10.0, reaction 4h.Centrifugal, washing precipitation is until pH reaches 7, and is centrifugal, obtains powder-product after the dry 24h of 80 ° of C.Agitation condition in the present embodiment is 600 rev/mins.
The pattern of the flower-shaped microballoon of porous hydroxyapatite for preparing in the present embodiment all is spheroidal, rough, median size is 2.5 μ m, dispersed fine, further observe and find, each spherical surface is porous, and the nanoparticle that forms these pore textures is assembled by the nanoparticle of sheet structure and formed, lamellar spacing 28nm, the diameter of the hole of composition are 260nm.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. the preparation method of the flower-shaped microballoon of porous hydroxyapatite, is characterized in that comprising the steps:
(1) CaO being added 80 ° of C distilled water be digested to mass concentration is 1%～10% Ca (OH)
2Slurries, digestion time guarantee CaO digestion fully more than 10h; Under room temperature, and in mechanical stirring to Ca (OH)
2Slurries pass into CO
2/ N
2Mixed gas, CO
2And N
2Mol ratio is 0.1～0.5, and speed is 1L/min, and pH value of reaction system reaches 7 o'clock stopped reaction; Then add Al (OH)
3Solution, the mol ratio of calcium and aluminium is at 5:1～50:1;
Add phosphate solution under (2) 60 ° of C agitation conditions, reaction is centrifugal after 2～4h, washing precipitation is until pH reaches 7, obtains the flower-shaped microballoon powder-product of porous hydroxyapatite after centrifugal, drying.
2. the preparation method of the flower-shaped microballoon of porous hydroxyapatite according to claim 1 is characterized in that: described phosphoric acid salt is a kind of in Sodium phosphate dibasic, sodium phosphate.
3. the preparation method of the flower-shaped microballoon of porous hydroxyapatite according to claim 1 is characterized in that: described step (1) is 200～600 rev/mins with agitation condition in step (2).
4. the preparation method of the flower-shaped microballoon of porous hydroxyapatite according to claim 1, it is characterized in that: in described step (2), adding NaOH solution to keep reacting system PH value in reaction process is 10.0.
5. flower-shaped microballoon of porous hydroxyapatite that the described method of claim 1 to 4 any one prepares, it is characterized in that: the flower-shaped microballoon of described porous hydroxyapatite all is spheroidal, and median size is 2～4 μ m; Each spherical surface is porous, and nanoparticle that these pore textures are sheet structure is assembled and to be formed, and lamellar spacing 20～30nm, the diameter of the hole of composition are 200～300nm.
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Cited By (2)
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| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN106115644A (en) * | 2016-06-24 | 2016-11-16 | 张文凯 | A kind of preparation method of hydroxyapatite structure |
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Application publication date: 20130508 |