CN101172592A - Hydroxyapatite micrometre tube and method of producing the same - Google Patents
Hydroxyapatite micrometre tube and method of producing the same Download PDFInfo
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- CN101172592A CN101172592A CNA2007100473128A CN200710047312A CN101172592A CN 101172592 A CN101172592 A CN 101172592A CN A2007100473128 A CNA2007100473128 A CN A2007100473128A CN 200710047312 A CN200710047312 A CN 200710047312A CN 101172592 A CN101172592 A CN 101172592A
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Abstract
The invention relates to a hydroxyapatite micrometer pipe and a preparation method thereof, and belongs to the biologic material field. The method is characterized in that water soluble calcium salt and acid phosphate are taken as raw material, water is taken as the dissolvent, N is added, N-dimethyl formamide is taken as addition agent, the materials are stirred at a room temperature, heat treatment for 12 to 72 hours under 120 to 200 DEG C is performed, and the product after heat treatment is separated, then cleaned and dried. The inner diameter of the hydroxyapatite micrometer pipe prepared by the method is 450 to 550 nm, the outer diameter is 1000 to 1200 nm, the length is 20 to 50 micrometers, and the hydroxyapatite micrometer pipe can be applied in the biologic material field. The invention has the advantages that the cost of the material is low, the process is simple, the operation is convenient, and the appearance can be controlled and so on.
Description
Technical field
The present invention relates to a kind of hydroxyapatite micrometre tube and preparation method thereof, more precisely relate to, belong to technical field of biological material by weakly alkaline additive preparation hydroxyapatite micro mist.
Background technology
Hydroxyapatite has excellent biological compatibility, has the chemical ingredients similar with tooth with people's bone, carrier, gas sensor, ion-exchange, catalyzer or the support of the catalyst etc. of doing bone alternate material, drug delivery commonly used.Existing preparation method comprises the precipitator method, solvent-thermal method, sol-gel method and microwave-assisted synthetic method.But the pattern of the hydroxyapatite that obtains is generally needle-like and bar-shaped, yet there are no the report that utilizes wet chemistry method to prepare tubulose pattern hydroxyapatite.
Summary of the invention
The object of the present invention is to provide a kind of hydroxyapatite micrometre tube and low cost simple preparation method thereof.
Technology of the present invention as shown in Figure 1.Concrete steps are:
1, the preparation of liquid-phase reaction system:
With water-soluble Ca salt (as CaCl
2, C
4H
6O
4CaH
2O, Ca (NO
3)
2) and acid phosphate (as NaH
2PO
4, KH
2PO
4, K
2HPO
4, Na
2HPO
4) be raw material, with water solvent, add additive N, dinethylformamide.Wherein, the mol ratio of water-soluble Ca salt and acid phosphate is 5: 3, N, and the mol ratio of dinethylformamide and water-soluble Ca salt is greater than 100: 1.Control water-soluble calcium salt concn is 0.01 mol～5.0 mol.
Stir under the room temperature, obtain suspension or uniform solution by stirring.
2, suspension or uniform solution are transferred in the reactor, carry out hydrothermal treatment consists at 120～200 ℃, heat treatment time is 12～72 hours.
3, the product in the liquid-phase reaction system after the solvent heat treatment is separated.
Isolating method comprises centrifugation, filters or staticly settles etc.Separated products is washed and drying treatment, promptly get the hydroxyapatite micro mist.
By X-ray powder diffraction and Infrared spectroscopy, resulting product is the hydroxyapatite of pure phase, does not have other things to exist mutually.Stereoscan photograph confirms that resulting hydroxyapatite is a micron tube.The internal diameter of pipe is 450～550 nanometers, and external diameter is 1000～1200 nanometers, and length is 30～50 microns.Size is relatively even, good dispersity.
Calcium salt and phosphoric acid salt are in the strong basicity environment, and pH is greater than 9, and the stable phase of products therefrom is hydroxyapatite; In sour environment, pH is less than 4.8, and the stable phase of products therefrom is secondary calcium phosphate.The reaction that calcium salt and phosphoric acid salt generate phosphatic rock is a replacement(metathesis)reaction, and nucleating growth is rapid.
The obtained hydroxyapatite of previous methods is nanometer rod and the acicular form of nanometer, and very difficult control obtains other forms.In order to control synthesizing hydroxylapatite, we have selected a kind of weakly alkaline organic bases---N, dinethylformamide.It slowly releases OH in reaction process
-Ion provides an alkaline environment.
Along with the carrying out of reaction, at N, under the dinethylformamide effect, the pH of reaction system gradually from acidity to neutrality to superalkalinity, products therefrom also from the secondary calcium phosphate to the secondary calcium phosphate and the mixture of hydroxyapatite again to the hydroxyapatite of pure phase.Secondary calcium phosphate forms hydroxyapatite by the dissolving recrystallize, and flaky secondary calcium phosphate helps to form the hydroxyapatite of one dimension (rod, line, pipe).N, dinethylformamide have played the effect of control hydroxyapatite nucleation and growth, thereby reach the purpose of control hydroxyapatite form.
Hydroxyapatite micropowder preparing process provided by the invention has the following advantages:
(1) advantages of good crystallization of product micro mist.
(2), can make the hydroxyapatite micro mist of different-shape and size by the suitable preparation condition of control.
(3) N, dinethylformamide play the effect of weak base, constitution controller and solvent simultaneously in reaction process, do not need to add in addition other tensio-active agent in the reaction process, and this can simplify production process greatly, reduces cost.
(4) raw material is cheap and easy to get, easy to operate, and preparation technology is simple, does not need cost and complex equipment.Be easy to realize suitability for industrialized production.
(5) the hydroxyapatite micrometre tube particle diameter of gained is even, and form is single, and good dispersity has the potential advantage on mechanical property.
Description of drawings
Fig. 1 is preparation technology's schema of hydroxyapatite micro mist.
Fig. 2 is the X-ray diffraction spectrogram of hydroxyapatite micrometre tube.
Fig. 3 is the hydroxyapatite micrometre tube stereoscan photograph.
Fig. 4 is the hydroxyapatite micrometre tube stereoscan photograph.
Fig. 5 is the infrared spectrum of hydroxyapatite micrometre tube.
Fig. 6 is the X-ray diffraction spectrogram of 160 ℃ of thermal responses 2 hours, 5 hours and the product that obtained in 12 hours.
Embodiment
Further specify embodiment and effect with the following example, but be not limited only to embodiment.
Embodiment 1
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 5mL distilled water, add 10mL N then, dinethylformamide obtains homodisperse suspension.Suspension is changed in the 20mL reactor over to sealing.Reactor is put into baking oven, 160 ℃ of insulations 24 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 2 times with dehydrated alcohol and distilled water respectively, 60 ℃ of vacuum-dryings.Fig. 2 is the X-ray diffraction spectrogram of the hydroxyapatite micrometre tube of present embodiment preparation, does not find the diffraction peak of any impurity in the spectrogram, illustrates that product is single-phase hydroxyapatite micrometre tube.Fig. 3 and 4 is its electron scanning micrograph, can clearly find out tubular structure.Fig. 5 is its infrared spectrogram, 3570cm
-1Be the characteristic peak of hydroxyapatite, further specifying resulting product is hydroxyapatite.
Embodiment 2
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 5mL distilled water, add 10mL N then, dinethylformamide obtains homodisperse suspension.Suspension is changed in the 20mL reactor over to sealing.Reactor is put into baking oven, 160 ℃ of insulations 12 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 2 times with dehydrated alcohol and distilled water respectively, and 60 ℃ of vacuum-dryings promptly obtain hydroxyapatite micrometre tube.Fig. 6 c is the X-ray diffraction spectrogram of the hydroxyapatite micrometre tube of present embodiment preparation, does not find the diffraction peak of any impurity in the spectrogram, illustrates that products therefrom is single-phase hydroxyapatite micrometre tube.The hydroxyapatite of present embodiment preparation is the micron tube structure.
Comparative Examples 1N, dinethylformamide are additive preparation secondary calcium phosphate nanometer sheet and hydroxyapatite nano rod
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 5mL distilled water, add 10mL N then, dinethylformamide obtains homodisperse suspension.Suspension is changed in the 20mL reactor over to sealing.Reactor is put into baking oven, 160 ℃ of insulations 5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product is used dehydrated alcohol and distilled water wash respectively 2 times, and 60 ℃ of vacuum-dryings promptly get secondary calcium phosphate nanometer sheet and hydroxyapatite nano rod.Fig. 6 b is the X-ray diffraction spectrogram of the product of present embodiment preparation, and spectrogram explanation products therefrom is the mixed phase of secondary calcium phosphate and hydroxyapatite.The stereoscan photograph of the product of present embodiment preparation, show its pattern be nanometer sheet and nanometer rod mixture mutually.The top of rod begins to form hollow tubular structure.
Comparative Examples 2 waters are that solvent prepares hydroxyapatite nano sheet and polyhedron
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 15mL distilled water, obtain homodisperse suspension.Suspension is changed in the 20mL reactor over to sealing.Reactor is put into baking oven, 160 ℃ of insulations 24 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product is used dehydrated alcohol and distilled water wash respectively 2 times, and 60 ℃ of vacuum-dryings promptly obtain hydroxyapatite nano sheet and polyhedron.Stereoscan photograph shows that the hydroxyapatite of this Comparative Examples preparation is nanometer sheet and polyhedral mixture.
Comparative Examples 3N, dinethylformamide are additive preparation hydroxyapatite micrometre rod
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 10mL distilled water, add 5mL N then, dinethylformamide obtains homodisperse suspension.Suspension is changed in the 20mL reactor over to sealing.Reactor is put into baking oven, 160 ℃ of insulations 24 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product is used dehydrated alcohol and distilled water wash respectively respectively 2 times, and 60 ℃ of vacuum-dryings promptly obtain the hydroxyapatite micrometre rod.Stereoscan photograph finds that the hydroxyapatite of this Comparative Examples preparation is a micron bar.
Comparative Examples 4N, dinethylformamide are additive preparation secondary calcium phosphate nanometer sheet
At room temperature, with 0.110g CaCl
2With 0.094g NaH
2PO
4Join in the 5mL distilled water, add 10mL N then, dinethylformamide obtains homodisperse suspension.Suspension is changed in the 20mL reactor,, sealing.Reactor is put into baking oven, 160 ℃ of insulations 2 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product is used dehydrated alcohol and distilled water wash respectively 2 times, and 60 ℃ of vacuum-dryings promptly get the secondary calcium phosphate nanometer sheet.Fig. 6 a is the X-ray diffraction spectrogram of the secondary calcium phosphate nanometer sheet of present embodiment preparation, does not find the diffraction peak of any impurity in the spectrogram, illustrates that product is single-phase secondary calcium phosphate nanometer sheet.Stereoscan photograph is found the secondary calcium phosphate nanometer sheet of this Comparative Examples preparation, and nanometer sheet is assembled into the pattern of pencil, and its diameter is about 50nm, and length is about 2 μ m.
Claims (6)
1. hydroxyapatite micrometre tube, the internal diameter that it is characterized in that micron tube is 450～550 nanometers, and external diameter is 1000～1200 nanometers, and length is 30～50 microns.
2. by the preparation method of the described hydroxyapatite micrometre tube of claim 1, it is characterized in that comprising the steps:
(1) be raw material with water-soluble Ca salt and acid phosphate, with water is solvent, add N, dinethylformamide is an additive, and wherein, the mol ratio of water-soluble Ca salt and acid phosphate is 5: 3, N, the mol ratio of dinethylformamide and water-soluble Ca salt is greater than 100: 1, and control water-soluble calcium salt concn is 0.01 mol～5.0 mol, stirs under the room temperature;
(2) step (1) solution is transferred in the reactor 120～200 ℃ of thermal treatments 12～72 hours;
(3) product in the liquid-phase reaction system after the solvent heat treatment is separated after scouring and drying.
3. by the preparation method of the described hydroxyapatite micrometre tube of claim 2, it is characterized in that described water-soluble Ca salt is CaCl
2Or C
4H
6O
4CaH
2O or Ca (NO
3)
2
4. by the preparation method of the described hydroxyapatite micrometre tube of claim 2, it is characterized in that described acid phosphate is NaH
2PO
4Or KH
2PO
4Or K
2HPO
4Or Na
2HPO
4
5. by the preparation method of claim 2 or 3 or 4 described hydroxyapatite micrometre tubes, it is characterized in that described separation method comprises centrifugation or filtering separation or staticly settles separation.
6. be used for biomaterial by the described a kind of hydroxyapatite micrometre tube of claim 1.
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| CN101927989A (en) * | 2010-06-04 | 2010-12-29 | 山东轻工业学院 | Method for preparing ordered nest-shaped porous hydroxylapatite material |
| CN101979312A (en) * | 2010-10-28 | 2011-02-23 | 中国科学院上海硅酸盐研究所 | Hydroxylapatite bionic structure material and preparation method thereof |
| CN101891174B (en) * | 2009-03-11 | 2011-11-02 | 北京林业大学 | Hydroxyapatite with hollow sphere structure and preparation method thereof |
| CN102515128A (en) * | 2011-11-07 | 2012-06-27 | 鲁东大学 | Preparation method for rodlike hydroxyapatite nano material |
| CN103110952A (en) * | 2013-03-05 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Microwave-assisted preparation method of hydroxylapatite nanometer structure porous microspheres |
| CN103950922A (en) * | 2014-04-28 | 2014-07-30 | 中南大学 | Preparation method of nano-hydroxyapatite/nano-hydroxyapatite gas sensing material |
| CN104220649A (en) * | 2012-04-09 | 2014-12-17 | 株式会社小糸制作所 | Apatite crystal |
| CN106744767A (en) * | 2016-12-21 | 2017-05-31 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite micrometre tube and its preparation method and application |
| CN107867677A (en) * | 2016-09-28 | 2018-04-03 | 深圳先进技术研究院 | One-dimensional calcium phosphate nano/micro materials and its preparation method and application |
| CN113264515A (en) * | 2021-05-19 | 2021-08-17 | 西北工业大学 | Nickel phosphate nanotube multi-stage assembly structure material and preparation method and application thereof |
| CN115536382A (en) * | 2022-09-28 | 2022-12-30 | 华南理工大学 | Method for in-situ construction of hydroxyapatite micro-nano hollow tube on surface of calcium-phosphorus-silicon ceramic |
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| CN101891174B (en) * | 2009-03-11 | 2011-11-02 | 北京林业大学 | Hydroxyapatite with hollow sphere structure and preparation method thereof |
| CN101927989A (en) * | 2010-06-04 | 2010-12-29 | 山东轻工业学院 | Method for preparing ordered nest-shaped porous hydroxylapatite material |
| CN101927989B (en) * | 2010-06-04 | 2012-03-21 | 山东轻工业学院 | Method for preparing ordered nest-shaped porous hydroxylapatite material |
| CN101979312A (en) * | 2010-10-28 | 2011-02-23 | 中国科学院上海硅酸盐研究所 | Hydroxylapatite bionic structure material and preparation method thereof |
| CN101979312B (en) * | 2010-10-28 | 2012-05-30 | 中国科学院上海硅酸盐研究所 | Hydroxylapatite bionic structure material and preparation method thereof |
| CN102515128A (en) * | 2011-11-07 | 2012-06-27 | 鲁东大学 | Preparation method for rodlike hydroxyapatite nano material |
| US9371231B2 (en) | 2012-04-09 | 2016-06-21 | Koito Manufacturing Co., Ltd. | Apatite crystal |
| CN104220649A (en) * | 2012-04-09 | 2014-12-17 | 株式会社小糸制作所 | Apatite crystal |
| CN103110952B (en) * | 2013-03-05 | 2014-09-10 | 中国科学院上海硅酸盐研究所 | Microwave-assisted preparation method of hydroxylapatite nanometer structure porous microspheres |
| CN103110952A (en) * | 2013-03-05 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Microwave-assisted preparation method of hydroxylapatite nanometer structure porous microspheres |
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| CN107867677B (en) * | 2016-09-28 | 2021-06-15 | 深圳先进技术研究院 | One-dimensional calcium phosphate nano/micron material and preparation method and application thereof |
| CN106744767A (en) * | 2016-12-21 | 2017-05-31 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite micrometre tube and its preparation method and application |
| CN106744767B (en) * | 2016-12-21 | 2019-01-08 | 中国科学院上海硅酸盐研究所 | The preparation method of hydroxyapatite micrometre tube |
| CN113264515A (en) * | 2021-05-19 | 2021-08-17 | 西北工业大学 | Nickel phosphate nanotube multi-stage assembly structure material and preparation method and application thereof |
| CN113264515B (en) * | 2021-05-19 | 2023-11-17 | 西北工业大学 | Nickel phosphate nanotube multistage assembly structure material and preparation method and application thereof |
| CN115536382A (en) * | 2022-09-28 | 2022-12-30 | 华南理工大学 | Method for in-situ construction of hydroxyapatite micro-nano hollow tube on surface of calcium-phosphorus-silicon ceramic |
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