CN101058416A - Method of preparing ordered nano hydroxyl apatite polycrystal powder - Google Patents
Method of preparing ordered nano hydroxyl apatite polycrystal powder Download PDFInfo
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Abstract
The invention discloses a making method of sequent hydroxy phosphorite polycrystalline powder and calcium phosphate, which comprises the following steps: mixing 30% 0. 00167mol calcium nitrate per ml water and 15-60% 0. 0033-0. 0667g sodium dodecylbenzene sulfonate per ml alcohol; placing the mixed solution in the flask with reflux device; adding the composite solution with 30% ammonium monohydric phosphate at 0. 01mol phosphor/ml water solution and 15-60% alcohol and the composite solution with 20% sodium hydroxide solution at 0. 05-0. 1g sodium per ml water and 10-40% alcohol; heating to the refluxing temperature at 88-92 deg. c to do hydrothermal reaction at 4-14h; centrifuging; separating; drying the white sediment under 60-80 deg. c; obtaining the product with good crystallizing degree, high-sequent (spatial symmetry) nanometer layered polycrystalline structure; simplifying the method and reducing the cost.
Description
Technical field
Technical scheme of the present invention relates to the phosphoric acid salt of calcium, specifically a kind of preparation method of ordered nano hydroxyl apatite polycrystal powder.
Background technology
The chemical structural formula of hydroxyapatite is Ca
10(PO
4)
6(OH)
2, be the main inorganic composition of people and vertebrates bone and tooth.Because it has good biocompatibility and surfactivity, be widely used as bioceramic material, chromatographic material, filtering material, sorbing material and solid support material.
The ordered nano-structure hydroxyapatite is spatially to be assembled in an orderly manner by nanometer hydroxyapatite monocrystalline unit, and the characteristics that its existing nanometer hydroxyapatite had are as high specific surface area, high reactive behavior; Have the characteristics that the preface nanostructure is had again concurrently, as special optics, electricity, magnetic property, so the ordered nano-structure hydroxyapatite is being with a wide range of applications aspect bionical preparation, biomedical material, nanometer enhancing and the catalysis.
Ordered nano-structure hydroxyapatite research at present is less, (Yao, J.; Tjandra, W.; Chen, Y.Z.; Tam, K.C.; Ma, J.; Soh, B.Hydroxyapatite nanostructure material derived using cationicsuffactant as a template, J.Mater.Chem.2003,13,3053.), the document has reported that a kind of is the method that template prepares orderly bar-shaped hydroxyapatite with the cats product, its nanocrystalline degree of order is lower, it is on the low side and have a tangible broadening to show as XRD small-angle diffraction peak intensity, and to have adopted price height, cats product that toxicity is big in this technology be template, complicated process of preparation, cost are higher.CN 200410071505.3 discloses the electrochemical preparation method of nano ordered hydroxy apatite coating, the nanometer hydroxyapatite electrochemical deposition is carried out in variation by control electrochemical deposition parameter, and crystal grain of nanometer hydroxylapatite being assembled in a different manner formed microscopic appearance is the nano ordered hydroxy apatite coating with secondary structure of flowers shape, vertical, micropore shape.This method is complex process not only, and lacks symmetry in the nano ordered hydroxy apatite that the makes distribution spatially.In addition, the degree of crystallinity of the nanometer hydroxyapatite of prior art preparation is on the low side, need improve degree of crystallinity, energy consumption height by calcining.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of ordered nano hydroxyl apatite polycrystal powder is provided, adopting the anion surfactant sodium laurylsulfonate is template, in ethanol-water system with the get everything ready hydroxyl apatite polycrystal powder of high-sequential, the symmetry of having living space nanometer laminated structure, better crystallinity degree of hydro-thermal legal system, to overcome existing preparing nano hydroxyapatite powder complex process, condition harshness and cost is higher, degree of crystallinity is on the low side and the hydroxide radical phosphorite nanocrystalline degree of order is lower or lack the shortcoming of spatial symmetry.
The present invention solves this technical problem the technical scheme that is adopted: the preparation method of ordered nano hydroxyl apatite polycrystal powder the steps include:
(1) nitrocalcite is soluble in water, make the ca nitrate soln that proportioning is 0.00167 molar nitric acid calcium/every ml water, in addition sodium laurylsulfonate is dissolved in the ethanol, making proportioning is 0.0033～0.0667 gram sodium laurylsulfonate/every milliliter of alcoholic acid sodium laurylsulfonate ethanolic soln, the two is preheating to 60 ℃ then, getting 30 parts of ca nitrate solns mixes with 15～60 parts of sodium laurylsulfonate ethanolic solns, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use;
(2) Secondary ammonium phosphate or primary ammonium phosphate are dissolved in the water, make solution containing phosphate with 0.001 mole of phosphorus/every ml water proportioning, optional wherein a kind of, get 30 parts, the ethanol that adds 15～60 parts again is mixed with Secondary ammonium phosphate or primary ammonium phosphate and alcoholic acid mixed solution, and is stand-by;
(3) with dissolution of sodium hydroxide in water, make 0.05～0.1 the gram sodium hydroxide/every ml water proportioning sodium hydroxide solution, get 20 parts, add 10～40 parts ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by;
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 88～92 ℃ of reflux temperatures, hydro-thermal reaction 4～14 hours stops to stir and heating;
(5) will go up step gained reactant more at room temperature left standstill 0～12 day, centrifugation, obtain white precipitate, then it was immersed in the deionized water 0～3 day, again through centrifugation, the gained white precipitate is 60～80 ℃ of oven dry down, and the time is 1～2 day, obtains the product ordered nano hydroxyl apatite polycrystal powder.
The umber of said components is volume parts, and used volume unit is identical in each step.
The invention has the beneficial effects as follows:
1. the resulting ordered nano hydroxyl apatite polycrystal powder of the inventive method is the pure ha with nano lamellar polycrystalline structure of high-sequential (being spatial symmetry).Shown in Fig. 2 a, the flake nano hydroxyapatite monocrystalline that thickness is about 1.6 nanometers in the product becomes the laminate structure of high-sequential along one dimension direction ordered arrangement, the repeat cycle of this laminate structure is about 3.6 nanometers, and the degree of order of the nanostructure of the resulting ordered nano hydroxyl apatite polycrystal powder of the inventive method (spatial symmetry) is very high.As shown in Figure 1, there is the feature small-angle diffraction in XRD, and diffraction peak intensity is very high, the diffraction peak of hydroxyapatite is very clear, sharp-pointed, illustrate that the hydroxylapatite crystal degree is fine, overcome existing nanometer hydroxyapatite degree of crystallinity shortcoming on the low side,, saved energy consumption so need not to improve degree of crystallinity by calcining.
2. in the inventive method, adopting the low anion surfactant sodium laurylsulfonate of toxicity to substitute the big cats product of toxicity is template, helps toxicological harmless production and environment protection.
3. in the inventive method, what adopt is that the alternative big ammoniacal liquor of toxicity of the less sodium hydroxide of toxicity is regulated the pH value, and in reaction process, one step of sodium hydroxide is added, overcome common needs in advance with ammoniacal liquor respectively to calcium salt soln and the phosphate solution cumbersome procedure of adjust pH respectively, simplified production technique.
4. the inventive method adopts and reacts under normal pressure, do not need the high-pressure reactor of the 2MPa of existing hydro-thermal synthetic technology requirement with upward pressure, the reaction reflux temperature is azeotropic temperature＜100 ℃ of ethanol-water mixed solvent, 200 ℃ of more common hydro-thermal synthesis temperatures are much lower, reduced energy consumption in a large number, what overcome that prior art hydro-thermal synthesizing hydroxylapatite exists needs high temperature, condition of high voltage usually, and product yield is on the low side, be prone to dephasign, as the shortcoming of secondary calcium phosphate.
5. raw material nitrocalcite, Secondary ammonium phosphate and the sodium hydroxide of the present invention's employing all belong to general chemistry reagent, and is cheap and easy to get.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is embodiment 1 a laminate hydroxyapatite powder XRD spectra, and wherein inserting figure is partial 5 times of enlarged views.
Fig. 2 is (a) lamellar hydroxylapatite transmission electron microscope photo among the embodiment 1, (b) selected area electron diffraction photo.
Fig. 3 is the formation principle schematic of the high-sequential nano lamellar hydroxylapatite of the inventive method.
Among the figure, the 1. double-deck phase template of tensio-active agent, 2. water layer, 3. hydroxyapatite platy-monocrystal, the 4. double-deck phase of tensio-active agent.
Embodiment
Fig. 3 illustrates the principle of the inventive method: cubes 1 representative of top is that anion surfactant sodium laurylsulfonate molecule forms the double-deck phase template of tensio-active agent by self-assembly among the figure.1 local amplifier section is the nanometer water layer 2 of this template, and wherein chemical reaction has taken place for nitrocalcite, Secondary ammonium phosphate and sodium hydroxide.The nucleating growth process that the arrow represents hydroxyapatite is carried out in this water layer among the figure, the cubes representative of below is the nanometer laminated structure polycrystalline aggregate that is formed by hydroxyapatite platy-monocrystal 3 and the double-deck arrangement of 4 high-sequentials (being spatial symmetry) mutually of tensio-active agent that finally obtains among the figure.
Embodiment 1
(1) 0.05mol nitrocalcite is dissolved in the beaker that fills 30mL water, in addition the 0.5g sodium laurylsulfonate is dissolved in and makes sodium laurylsulfonate ethanolic soln mixed solution in the beaker that fills the 30mL ethanolic soln, mix after then the two being preheating to 60 ℃, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use.
(2) the 0.03mol Secondary ammonium phosphate is dissolved in the 30mL water, adds 30mL ethanol again, be mixed with Secondary ammonium phosphate and alcoholic acid mixed solution, stand-by.
(3) with the 2g dissolution of sodium hydroxide in 20mL water, add 20mL ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by.
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 90 ℃ of reflux temperatures, hydro-thermal reaction 14 hours stops to stir and heating.
(5) will go up the step products therefrom again and at room temperature leave standstill 12 days, centrifugation obtains white precipitate, then it was immersed in the deionized water 3 days, again through centrifugation, the gained white precipitate is 60 ℃ of oven dry down, time is 1 day, obtains product ordered nano hydroxyl apatite polycrystal powder 3g.
Through the XRD test, the product ordered nano hydroxyl apatite polycrystal powder is the nano lamellar hydroxylapatite of high-sequential (being spatial symmetry).Small-angle diffraction peak (100) among Fig. 1, (200), (300), (400) and (500) show that there is high-sequential (being spatial symmetry) nanometer laminated structure in the product ordered nano hydroxyl apatite polycrystal powder; Wide-angle diffraction peak among Fig. 1 insertion figure shows that the product ordered nano hydroxyl apatite polycrystal powder is the pure ha nanocrystal, does not contain other dephasign.Three main diffraction peaks (211) of product ordered nano hydroxyl apatite polycrystal powder, (112) and (300) have certain broadening phenomenon, illustrated that hydroxyapatite crystal grain is nanocrystalline, these diffraction peaks are clear, sharp-pointed simultaneously, illustrate that the degree of crystallinity of this nanometer hydroxyapatite is fine.
Observed the nanometer laminated structure of the high-sequential (spatial symmetry) of product ordered nano hydroxyl apatite polycrystal powder again through the TEM test.Fig. 2 a is the side photo of the nanometer laminated structure of product ordered nano hydroxyl apatite polycrystal powder, as can be seen, dark hydroxyapatite is arranged in the nano array structure of high-sequential (spatial symmetry) in an orderly manner, the arrow indication is a repeat cycle structure, and wherein hydroxyapatite platy-monocrystal thickness is about 1.6 nanometers; Fig. 2 b is the selected area electron diffraction photo, and diffraction is ring-type clearly, and the hydroxyapatite that this nanometer laminated structure is described is a polycrystalline aggregate.
Secondary ammonium phosphate in the step (2) among the embodiment 1 is replaced with primary ammonium phosphate, and other steps are with embodiment 1.Obtain product with embodiment 1.
Embodiment 3
The ethanolic soln consumption of step (1) among the embodiment 1 and the ethanol consumption of step (2) (3) are reduced by half, and reflux temperature is 92 ℃, and other steps are with embodiment 1.Obtain product with embodiment 1.
The ethanolic soln consumption of step (1) among the embodiment 1 and the ethanol consumption of step (2) (3) are doubled, and reflux temperature is 88 ℃, and other steps are with embodiment 1.Obtain product embodiment 1.
(1) 0.05mol nitrocalcite is dissolved in the beaker that fills 30mL water, in addition the 0.1g sodium laurylsulfonate is dissolved in and makes sodium laurylsulfonate ethanolic soln mixed solution in the beaker that fills the 30mL ethanolic soln, mix after then the two being preheating to 60 ℃, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use.
(2) the 0.03mol Secondary ammonium phosphate is dissolved in the 30mL water, adds 30mL ethanol again, be mixed with Secondary ammonium phosphate and alcoholic acid mixed solution, stand-by.
(3) with the 1g dissolution of sodium hydroxide in 20mL water, add 20mL ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by.
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 90 ℃ of reflux temperatures, hydro-thermal reaction 9 hours stops to stir and heating.
(5) will go up the step products therefrom again and at room temperature leave standstill 6 days, centrifugation obtains white precipitate, then it was immersed in the deionized water 1.5 days, again through centrifugation, the gained white precipitate is 70 ℃ of oven dry down, time is 1.5 days, obtains product ordered nano hydroxyl apatite polycrystal powder 3g.
Embodiment 6
(1) 0.05mol nitrocalcite is dissolved in the beaker that fills 30mL water, in addition the 1g sodium laurylsulfonate is dissolved in and makes sodium laurylsulfonate ethanolic soln mixed solution in the beaker that fills the 30mL ethanolic soln, mix after then the two being preheating to 60 ℃, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use.
(2) the 0.03mol Secondary ammonium phosphate is dissolved in the 30mL water, adds 30mL ethanol again, be mixed with Secondary ammonium phosphate and alcoholic acid mixed solution, stand-by.
(3) with the 1.5g dissolution of sodium hydroxide in 20mL water, add 20mL ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by.
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 90 ℃ of reflux temperatures, hydro-thermal reaction 4 hours stops to stir and heating.
(5) will go up the centrifugation at room temperature of step products therefrom again, and obtain white precipitate, and then the gained white precipitate be dried down at 80 ℃, the time is 2 days, obtains product ordered nano hydroxyl apatite polycrystal powder 3g.
Embodiment 7
(1) 0.05mol nitrocalcite is dissolved in the beaker that fills 30mL water, in addition the 2g sodium laurylsulfonate is dissolved in and makes sodium laurylsulfonate ethanolic soln mixed solution in the beaker that fills the 30mL ethanolic soln, mix after then the two being preheating to 60 ℃, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use.
(2) the 0.03mol Secondary ammonium phosphate is dissolved in the 30mL water, adds 30mL ethanol again, be mixed with Secondary ammonium phosphate and alcoholic acid mixed solution, stand-by.
(3) with the 2g dissolution of sodium hydroxide in 20mL water, add 20mL ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by.
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 90 ℃ of reflux temperatures, hydro-thermal reaction 14 hours stops to stir and heating.
(5) will go up the step products therefrom again and at room temperature leave standstill 12 days, centrifugation obtains white precipitate, then it was immersed in the deionized water 3 days, again through centrifugation, the gained white precipitate is 60 ℃ of oven dry down, time is 1 day, obtains product ordered nano hydroxyl apatite polycrystal powder 3g.
Claims (1)
1. the preparation method of ordered nano hydroxyl apatite polycrystal powder is characterized in that step is:
(1) nitrocalcite is soluble in water, make the ca nitrate soln that proportioning is 0.00167 molar nitric acid calcium/every ml water, in addition sodium laurylsulfonate is dissolved in the ethanol, making proportioning is 0.0033～0.0667 gram sodium laurylsulfonate/every milliliter of alcoholic acid sodium laurylsulfonate ethanolic soln, the two is preheating to 60 ℃ then, getting 30 parts of ca nitrate solns mixes with 15～60 parts of sodium laurylsulfonate ethanolic solns, add and have in the flask of reflux, induction stirring is even under 60 ℃ of conditions, heat preservation for standby use;
(2) Secondary ammonium phosphate or primary ammonium phosphate are dissolved in the water, make solution containing phosphate with 0.001 mole of phosphorus/every ml water proportioning, optional wherein a kind of, get 30 parts, the ethanol that adds 15～60 parts again is mixed with Secondary ammonium phosphate or primary ammonium phosphate and alcoholic acid mixed solution, and is stand-by;
(3) with dissolution of sodium hydroxide in water, make 0.05～0.1 the gram sodium hydroxide/every ml water proportioning sodium hydroxide solution, get 20 parts, add 10～40 parts ethanol again, be mixed with the sodium hydroxide alcohol mixeding liquid, stand-by;
(4) liquid mixture prepared in step (2), (3) is preheating to 60 ℃, joins fast successively in the flask in the step (1), be warming up to 88～92 ℃ of reflux temperatures, hydro-thermal reaction 4～14 hours stops to stir and heating;
(5) will go up step gained reactant more at room temperature left standstill 0～12 day, centrifugation, obtain white precipitate, then it was immersed in the deionized water 0～3 day, again through centrifugation, the gained white precipitate is 60～80 ℃ of oven dry down, and the time is 1～2 day, obtains the product ordered nano hydroxyl apatite polycrystal powder;
The umber of said components is volume parts, and used volume unit is identical in each step.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759170B (en) * | 2009-12-23 | 2011-07-06 | 天津大学 | Magnetic nano sheet-shaped hydroxyapatite and preparation method and application thereof |
| CN103572346A (en) * | 2012-07-27 | 2014-02-12 | 北京纳通科技集团有限公司 | Hydroxyapatite surface film and preparation method thereof |
| CN104623694A (en) * | 2015-02-06 | 2015-05-20 | 天津大学 | Method for preparing polyethyleneimine/ lamellar hydroxyapatite/ 5-fluorouracil/DNA compound with traceability |
| CN107899079A (en) * | 2017-11-20 | 2018-04-13 | 华东交通大学 | Nano sheet-shaped hydroxyapatite/synthesized thin film and preparation method with brick mud structure |
| CN107934932A (en) * | 2017-12-19 | 2018-04-20 | 安徽理工大学 | A kind of method for preparing hydroxyapatite using discarded powder of lacquer putty for use on |
| CN111115597A (en) * | 2018-10-30 | 2020-05-08 | 天津工业大学 | Preparation method of porous nano hydroxyapatite based on aromatic acid salt |
-
2007
- 2007-05-24 CN CNB2007101072261A patent/CN100482578C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759170B (en) * | 2009-12-23 | 2011-07-06 | 天津大学 | Magnetic nano sheet-shaped hydroxyapatite and preparation method and application thereof |
| CN103572346A (en) * | 2012-07-27 | 2014-02-12 | 北京纳通科技集团有限公司 | Hydroxyapatite surface film and preparation method thereof |
| CN103572346B (en) * | 2012-07-27 | 2015-11-25 | 北京纳通科技集团有限公司 | Hydroxyapatite surface film and preparation method thereof |
| CN104623694A (en) * | 2015-02-06 | 2015-05-20 | 天津大学 | Method for preparing polyethyleneimine/ lamellar hydroxyapatite/ 5-fluorouracil/DNA compound with traceability |
| CN107899079A (en) * | 2017-11-20 | 2018-04-13 | 华东交通大学 | Nano sheet-shaped hydroxyapatite/synthesized thin film and preparation method with brick mud structure |
| CN107934932A (en) * | 2017-12-19 | 2018-04-20 | 安徽理工大学 | A kind of method for preparing hydroxyapatite using discarded powder of lacquer putty for use on |
| CN111115597A (en) * | 2018-10-30 | 2020-05-08 | 天津工业大学 | Preparation method of porous nano hydroxyapatite based on aromatic acid salt |
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