CN106927443A - A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof - Google Patents
A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof Download PDFInfo
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- CN106927443A CN106927443A CN201710284265.2A CN201710284265A CN106927443A CN 106927443 A CN106927443 A CN 106927443A CN 201710284265 A CN201710284265 A CN 201710284265A CN 106927443 A CN106927443 A CN 106927443A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to a kind of three-dimensional porous nano hydroxyapatite and preparation method thereof.Its technical scheme is：During carboxymethylcellulose sodium solution added into ball mill, ball milling, then to adding calcium salt soln, ball milling to obtain mixed liquor in ball mill.By in mixed liquor immigration container, under agitation to phosphate solution and ammoniacal liquor is added in mixed liquor, presoma I is obtained；Phosphate solution is 9.50 ~ 11.00 with the pH value of the mixed solution of ammoniacal liquor.Presoma I is moved into ball milling in ball mill, presoma II is obtained；Presoma II is moved into closed vessel again, is aged, obtain presoma III；Presoma III is refrigerated to solid-state, freeze-drying is carried out, presoma IV is obtained.Presoma IV is calcined, three-dimensional porous nano hydroxyapatite is obtained.The characteristics of present invention has process is simple, with low cost, environmental protection and raw material availability high, prepared product appearance and size is homogeneous, size range is narrow, porosity is high and specific surface area is big.
Description
Technical field
The invention belongs to porous nano hydroxyapatite technical field.Specifically related to a kind of three-dimensional porous nano hydroxy-apatite
Stone and preparation method thereof.
Background technology
Porous nano hydroxyapatite belongs to the environmentally conscious materialses and biomaterial of a kind of better performances, is preparing apatite mistake
Template is added in journey, template is removed by high-temperature roasting, the porous nanometer material with apatite as skeleton is finally obtained.It is many
Hole nano-apatite is widely used in dentistry, lift face section, bone graft material and pharmaceutical carrier, with good as biomaterial
Biocompatibility, non-toxic and high biodegradability；As environmentally conscious materialses, adsorbent is mainly used as, is widely used in treatment
The environmental pollutions such as heavy metal in waste water, the features such as with low cost, wide material sources and high treating effect.
" a kind of PEG compound systems hydrothermal preparing process of nanometer hydroxyapatite "（CN201410787214.8）Using double
Hydrothermal template preparation method, obtains nanometer hydroxyapatite, has the advantages that process is simple, with low cost, green safety.But by
Hydroxyapatite is processed in the method using high temperature drying, has very havoc, obtained hydroxyapatite to the structure of material
Appearance and size heterogeneity, porosity are small and without three-dimensional porous structure.
" a kind of preparation method of nano hydroxyapatite powder "（CN200910265055.4）Hydroxyl is prepared using template
Base apatite, is dried with freeze-drying, obtains the spherical or rod-like nano hydroxy apatite powder of good dispersion, is prepared
Method is simple, with short production cycle and nontoxic pollution-free.But hydroxyapatite appearance and size heterogeneity, porosity prepared by the method
Small and no three-dimensional porous structure.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide a kind of process is simple, with low cost, green safety and
Raw material availability three-dimensional porous nano hydroxyapatite preparation method high, the three-dimensional porous nano hydroxyl phosphorus prepared with the method
Lime stone porosity is high, appearance and size is homogeneous, specific surface area is larger and size range is narrower.
To achieve the above object, the technical solution adopted by the present invention is comprised the concrete steps that：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 10 ~ 40min of ball milling；Added in the ball mill again
Calcium salt soln, 10 ~ 60min of ball milling, obtains final product mixed liquor.Wherein：Calcium constituent in the calcium salt soln: the carboxymethylcellulose calcium
The mol ratio of the sodium carboxymethylcellulose in sodium solution is（8~24）∶1.
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: phosphorus in phosphate solution
The mol ratio of element is 1.67: 1；Under agitation to the mixing that the phosphate solution and ammoniacal liquor are added in the mixed liquor
Solution, obtains presoma I；The phosphate solution is 9.50 ~ 11.00 with the pH value of the mixed solution of ammoniacal liquor.
Step 3, presoma I moves into ball mill, 10 ~ 60min of ball milling obtains presoma II；Again by the presoma
II is moved into closed vessel, and 24 ~ 32h is aged under the conditions of 28 ~ 38 DEG C, obtains presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48 ~ 56h of freeze-drying obtains presoma IV.
Step 4, the presoma IV is calcined 2 ~ 3h under the conditions of 700 ~ 800 DEG C, three-dimensional porous nano hydroxyl phosphorus is obtained
Lime stone.
Calcium salt in the calcium salt soln is calcium nitrate or is calcium chloride.
Phosphate in the phosphate solution is the one kind in ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate and phosphoric acid.
Due to using above-mentioned technical proposal, the beneficial effects of the invention are as follows：
The present invention is using three sections of preparation flows of ball milling-ageing-drying-roasting, process is simple.Reaction is participated in preparation process
Reactant reacts complete, and product only has hydroxyapatite and the waste water containing ammonium nitrate, and wherein sodium carboxymethylcellulose exists
Roasting process is with CO2And H2The form removal of O, the water containing ammonium nitrate, without influence, can be recycled on preparation process of the present invention,
Ammonium nitrate can be used as agrochemical raw material, therefore raw material availability is high, with low cost and green safety.
The method that the present invention is combined using mechanochemistry and template, prepares hydroxyapatite in ball mill, adds mould
Plate agent makes product turn into the nano material for having three-dimensional porous structure, and porosity is high and specific surface area is big, and mechanochemistry treatment makes original
Material is fully mixed and reaction is complete, makes the uniform size range of product appearance and size narrow, the particle diameter of made product for 100 ~
200nm.In addition, the present invention uses Freeze Drying Technique, the structure of hydroxyapatite can be effectively protected.
Therefore, the characteristics of present invention has process is simple, with low cost, environmental protection and raw material availability high, it is prepared
Three-dimensional porous nano hydroxyapatite appearance and size it is homogeneous, size range is narrow, porosity is high and specific surface area is big.
Brief description of the drawings
Fig. 1 is a kind of SEM figures of three-dimensional porous nano hydroxyapatite prepared by the present invention；
Fig. 2 is the SEM figures of the plane of disruption of three-dimensional porous nano hydroxyapatite shown in Fig. 1.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
Embodiment 1
A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof.Preparation method described in the present embodiment is comprised the concrete steps that：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 10 ~ 25min of ball milling；Added in the ball mill again
Calcium salt soln, 10 ~ 30min of ball milling, obtains final product mixed liquor.Wherein：Calcium constituent in the calcium salt soln: the carboxymethylcellulose calcium
The mol ratio of the sodium carboxymethylcellulose in sodium solution is（8~12）∶1.
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: phosphorus in phosphate solution
The mol ratio of element is 1.67: 1；Under agitation to the mixing that the phosphate solution and ammoniacal liquor are added in the mixed liquor
Solution, obtains presoma I；The phosphate solution is 9.50 ~ 10 with the pH value of the mixed solution of ammoniacal liquor.
Step 3, presoma I moves into ball mill, 10 ~ 30min of ball milling obtains presoma II；Again by the presoma
II is moved into closed vessel, and 24 ~ 32h is aged under the conditions of 28 ~ 38 DEG C, obtains presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48 ~ 56h of freeze-drying obtains presoma IV.
Step 4, the presoma IV is calcined 2 ~ 3h under the conditions of 700 ~ 740 DEG C, three-dimensional porous nano hydroxyl phosphorus is obtained
Lime stone.
Calcium salt in the calcium salt soln is calcium nitrate.
Phosphate in the phosphate solution is ammonium dihydrogen phosphate.
The particle diameter of three-dimensional porous nano hydroxyapatite manufactured in the present embodiment is 100 ~ 200nm.
Embodiment 2
A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof.Preparation method described in the present embodiment is comprised the concrete steps that：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 15 ~ 30min of ball milling；Added in the ball mill again
Calcium salt soln, 20 ~ 40min of ball milling, obtains final product mixed liquor.Wherein：Calcium constituent in the calcium salt soln: the carboxymethylcellulose calcium
The mol ratio of the sodium carboxymethylcellulose in sodium solution is（12~16）∶1.
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: phosphorus in phosphate solution
The mol ratio of element is 1.67: 1；Under agitation to the mixing that the phosphate solution and ammoniacal liquor are added in the mixed liquor
Solution, obtains presoma I；The phosphate solution is 9.90 ~ 10.4 with the pH value of the mixed solution of ammoniacal liquor.
Step 3, presoma I moves into ball mill, 20 ~ 40min of ball milling obtains presoma II；Again by the presoma
II is moved into closed vessel, and 24 ~ 32h is aged under the conditions of 28 ~ 38 DEG C, obtains presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48 ~ 56h of freeze-drying obtains presoma IV.
Step 4, the presoma IV is calcined 2 ~ 3h under the conditions of 720 ~ 760 DEG C, three-dimensional porous nano hydroxyl phosphorus is obtained
Lime stone.
Calcium salt in the calcium salt soln is calcium chloride.
Phosphate in the phosphate solution is ammonium phosphate.
The particle diameter of three-dimensional porous nano hydroxyapatite manufactured in the present embodiment is 100 ~ 200nm.
Embodiment 3
A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof.Preparation method described in the present embodiment is comprised the concrete steps that：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 20 ~ 35min of ball milling；Added in the ball mill again
Calcium salt soln, 30 ~ 50min of ball milling, obtains final product mixed liquor.Wherein：Calcium constituent in the calcium salt soln: the carboxymethylcellulose calcium
The mol ratio of the sodium carboxymethylcellulose in sodium solution is（16~20）∶1.
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: phosphorus in phosphate solution
The mol ratio of element is 1.67: 1；Under agitation to the mixing that the phosphate solution and ammoniacal liquor are added in the mixed liquor
Solution, obtains presoma I；The phosphate solution is 10.3 ~ 10.7 with the pH value of the mixed solution of ammoniacal liquor.
Step 3, presoma I moves into ball mill, 30 ~ 50min of ball milling obtains presoma II；Again by the presoma
II is moved into closed vessel, and 24 ~ 32h is aged under the conditions of 28 ~ 38 DEG C, obtains presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48 ~ 56h of freeze-drying obtains presoma IV.
Step 4, the presoma IV is calcined 2 ~ 3h under the conditions of 740 ~ 780 DEG C, three-dimensional porous nano hydroxyl phosphorus is obtained
Lime stone.
Calcium salt in the calcium salt soln is calcium nitrate.
Phosphate in the phosphate solution is ammonium hydrogen phosphate.
Fig. 1 and Fig. 2 are a kind of SEM figures of three-dimensional porous nano hydroxyapatite manufactured in the present embodiment, by particle diameter point
Cloth software for calculation Nano Measurer, the particle diameter for obtaining product shown in the present embodiment is 100 ~ 200nm.
Embodiment 4
A kind of three-dimensional porous nano hydroxyapatite and preparation method thereof.Preparation method described in the present embodiment is comprised the concrete steps that：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 25 ~ 40min of ball milling；Added in the ball mill again
Calcium salt soln, 40 ~ 60min of ball milling, obtains final product mixed liquor.Wherein：Calcium constituent in the calcium salt soln: the carboxymethylcellulose calcium
The mol ratio of the sodium carboxymethylcellulose in sodium solution is（20~24）∶1.
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: phosphorus in phosphate solution
The mol ratio of element is 1.67: 1；Under agitation to the mixing that the phosphate solution and ammoniacal liquor are added in the mixed liquor
Solution, obtains presoma I；The phosphate solution is 10.6 ~ 11.0 with the pH value of the mixed solution of ammoniacal liquor.
Step 3, presoma I moves into ball mill, 40 ~ 60min of ball milling obtains presoma II；Again by the presoma
II is moved into closed vessel, and 24 ~ 32h is aged under the conditions of 28 ~ 38 DEG C, obtains presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48 ~ 56h of freeze-drying obtains presoma IV.
Step 4, the presoma IV is calcined 2 ~ 3h under the conditions of 760 ~ 800 DEG C, three-dimensional porous nano hydroxyl phosphorus is obtained
Lime stone.
Calcium salt in the calcium salt soln is calcium chloride.
Phosphate in the phosphate solution is phosphoric acid.
The particle diameter of three-dimensional porous nano hydroxyapatite manufactured in the present embodiment is 100 ~ 200nm.
This specific embodiment compared with prior art, has the advantages that：
This specific embodiment is using three sections of preparation flows of ball milling-ageing-drying-roasting, process is simple.Join in preparation process
Reactant with reaction reacts complete, and product only has hydroxyapatite and the waste water containing ammonium nitrate, and wherein carboxymethyl is fine
The plain sodium of dimension is in roasting process with CO2And H2The form removal of O, the water containing ammonium nitrate is to this specific embodiment preparation process without shadow
Ring, can recycle, ammonium nitrate can be used as agrochemical raw material, therefore raw material availability is high, with low cost and green safety.
The method that this specific embodiment is combined using mechanochemistry and template, prepares hydroxy-apatite in ball mill
Stone, adds template product is turned into the nano material for having three-dimensional porous structure, and porosity is high and specific surface area is big, mechanochemistry
Treatment makes raw material fully mix and reacts complete, makes the uniform size range of product appearance and size narrow.In addition, this specific embodiment party
Formula uses Freeze Drying Technique, can effectively protect the structure of hydroxyapatite.
Fig. 1 is a kind of SEM figures of three-dimensional porous nano hydroxyapatite prepared by embodiment 3；Fig. 2 is three-dimensional shown in Fig. 1
The SEM figures of the plane of disruption of porous nano hydroxyapatite.Be can be seen that from Fig. 1 and Fig. 2：Shown product appearance and size is homogeneous, chi
Very little narrow range, porosity are high and specific surface area is big.Further accordance with Fig. 1 and Fig. 2 and by particle diameter distribution software for calculation Nano
Measurer, the particle diameter for obtaining made product is 100 ~ 200nm.
Therefore, this specific embodiment has process is simple, with low cost, environmental protection and raw material availability spy high
Point, prepared three-dimensional porous nano hydroxyapatite appearance and size is homogeneous, size range is narrow, porosity is high and specific surface area
Greatly.
Claims (4)
1. a kind of preparation method of three-dimensional porous nano hydroxyapatite, it is characterised in that be the step of the preparation method：
Step one, by carboxymethylcellulose sodium solution add ball mill in, 10~40min of ball milling；Add in the ball mill again
Enter calcium salt soln, 10~60min of ball milling obtains final product mixed liquor；Wherein：Calcium constituent in the calcium salt soln: the carboxymethyl is fine
The mol ratio of the sodium carboxymethylcellulose in the plain sodium solution of dimension is (8~24): 1；
Step 2, by the mixed liquor move into container in, by the calcium constituent in the calcium salt soln: P elements in phosphate solution
Mol ratio be 1.67: 1；Under agitation to adding the phosphate solution molten with the mixing of ammoniacal liquor in the mixed liquor
Liquid, obtains presoma I；The phosphate solution is 9.50~11.00 with the pH value of the mixed solution of ammoniacal liquor；
Step 3, presoma I moves into ball mill, 10~60min of ball milling obtains presoma II；Again by the presoma II
Move into closed vessel, 24~32h is aged under the conditions of 28~38 DEG C, obtain presoma III；Then it is the presoma III is cold
Freeze to solid-state, move into freeze drier, 48~56h of freeze-drying obtains presoma IV；
Step 4, the presoma IV is calcined 2~3h under the conditions of 700~800 DEG C, three-dimensional porous nano hydroxy-apatite is obtained
Stone.
2. the preparation method of three-dimensional porous nano hydroxyapatite according to claim 1, it is characterised in that the calcium salt
Calcium salt in solution is calcium nitrate or is calcium chloride.
3. the preparation method of three-dimensional porous nano hydroxyapatite according to claim 1, it is characterised in that the phosphoric acid
Phosphate in salting liquid is the one kind in ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate and phosphoric acid.
4. a kind of three-dimensional porous nano hydroxyapatite, it is characterised in that the three-dimensional porous nano hydroxyapatite is according to power
Profit requires the three-dimensional porous nano prepared by the preparation method of three-dimensional porous nano hydroxyapatite any one of 1~3
Hydroxyapatite.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584899A (en) * | 2018-08-01 | 2018-09-28 | 武汉科技大学 | A kind of porous prilled nanometer hydroxyapatite and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883740A (en) * | 2014-12-18 | 2016-08-24 | 江南大学 | PEG compound system hydrothermal preparation method for nano-hydroxyapatite |
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2017
- 2017-04-26 CN CN201710284265.2A patent/CN106927443A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883740A (en) * | 2014-12-18 | 2016-08-24 | 江南大学 | PEG compound system hydrothermal preparation method for nano-hydroxyapatite |
Non-Patent Citations (1)
| Title |
|---|
| 刘威等: "结构可调控纳米羟基磷灰石的制备研究", 《人工晶体学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584899A (en) * | 2018-08-01 | 2018-09-28 | 武汉科技大学 | A kind of porous prilled nanometer hydroxyapatite and preparation method thereof |
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