CN105217593B - A kind of preparation method of the sub- nano wire of flexible ultra-fine hydroxyapatite - Google Patents
A kind of preparation method of the sub- nano wire of flexible ultra-fine hydroxyapatite Download PDFInfo
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- CN105217593B CN105217593B CN201510605584.XA CN201510605584A CN105217593B CN 105217593 B CN105217593 B CN 105217593B CN 201510605584 A CN201510605584 A CN 201510605584A CN 105217593 B CN105217593 B CN 105217593B
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Abstract
The invention discloses a kind of preparation method with the sub- nano wire of flexible ultra-fine hydroxyapatite, it is in oleic acid, the mixed liquor of second alcohol and water, add calcium saline solution, aqueous phosphatic, rare earth nitrate aqueous solution, 7 ~ 15 d are stood after stirring in 0 DEG C~30 DEG C of environment, the flexible ultra-fine sub- nano wire with hydroxyapatite characteristic is obtained.Nano wire prepared by the present invention is flexible superfine nanowire, it is used as new calcium Apatite materials, available for inorganic materials, or for constructing the bio-medical compositions such as new artificial bone, bone cement with organic macromolecule assembling, improve the controlled degradation of composite.
Description
Technical field
The present invention relates to a kind of preparation method of the flexible sub- nano wire of ultra-fine hydroxyapatite.
Background technology
Nanometer hydroxyapatite（Ca10(OH)2(PO4)6 , HAp）It is a kind of biomaterial, collosol and gel can be passed through
Prepared by method, hydro-thermal method, supercritical ultrasonics technology, a variety of methods such as biomineralization method, hydroxyapatite belongs to hexagonal crystal system in addition, is a kind of
Outstanding ion doping matrix, is applicable to most of anions and canons doping.By the doping of foreign ion, hydroxyl can be enriched
The species and performance of apatite.The hydroxyapatite nano-structure or hyperfine structure generally prepared, no matter pattern and size are big
It is small, all with strong rigidity characteristic.
The content of the invention
It is an object of the invention to provide a kind of low temperature mineralising of the flexible ultra-fine sub- nano wire with hydroxyapatite characteristic
Preparation method.
The implementation process of the present invention is as follows：
A kind of preparation method of the sub- nano wire of flexible ultra-fine hydroxyapatite, its in the mixed solution of oleic acid and ethanol,
Calcium saline solution, aqueous phosphatic and rare earth nitrate aqueous solution are added, the volume ratio for making oleic acid, ethanol and water is 1: (2~
8):(2 ~ 8), stand 7 ~ 15 days at 0 DEG C~30 DEG C after stirring and obtain the sub- nano wire of flexible ultra-fine hydroxyapatite.
Above-mentioned calcium salt is calcium nitrate；Phosphate is selected from sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate；Calcium salt with it is phosphatic
Mol ratio is 1:1.67.
The rare earth nitrades are the nitrate of trivalent rare earth, such as lanthanum nitrate, cerous nitrate, neodymium nitrate, gadolinium nitrate, nitric acid
Europium, terbium nitrate, ytterbium nitrate；The mol ratio of rare earth nitrades and calcium salt is (0.05 ~ 0.2):1.
Above-mentioned preparation method, the end-product obtained for several times using hexamethylene and ethanol cyclic washing, hexamethylene is detergent,
Ethanol is to help precipitating reagent.
The sub- nanowire diameter of flexible ultra-fine hydroxyapatite prepared by above-mentioned preparation method is 0.6 ~ 0.8 nm, and length is
0.3 ~ 5μm。
The ionic radius of trivalent rare earth ionses is comparable to the calcium ion radius in hydroxyapatite crystal, therefore can be easily
Replace the calcium ion combined with phosphate radical.In addition, trivalent rare earth ionses chemical valence is higher than divalent calcium ions, therefore bonding that more can be good
Template effect of polymeric anion in anionic group, enhancing soft template reaction system.The present invention utilizes trivalent rare earth ionses
Above-mentioned two feature, in conjunction with finite field growth characteristic nanocrystalline in low temperature mineralization process, chooses oil mixing with water mineralising reaction
System low temperature mineralising prepares apatite calcium, obtains a kind of flexible ultra-fine sub- nano wire with hydroxyapatite characteristic, enriches
The species of apatite calcium and potential use.
The positive effect of the present invention：Original of the invention based on hydroxylapatite biology mineralising and foreign ion doping vario-property
Reason, and it is higher than divalent calcium ions using trivalent rare earth ionses chemical valence, the more preferable bonded anionic group of energy, enhancing soft template is anti-
Template effect of polymeric anion in system is answered, oleic acid, the mineralising reaction system of second alcohol and water is chosen, obtains at low ambient temperatures
Obtained the flexible superfine nanowire of the calcium phosphate Subnano-class containing rare earth element with hydroxyapatite characteristic.Preparation side of the invention
Method raw material is cheap and easy to get, and reaction condition is gentle, and synthesis technique simply easily realizes that reaction cost is low, and technique amplification is easy and reappears
Performance is good, and product quality is stable；The flexible ultra-fine Asia containing rare earth element with hydroxyapatite characteristic prepared by this method
Nano wire can as new calcium Apatite materials, for inorganic material film, or for organic macromolecule assembling construct new
The bio-medical composition such as artificial bone, bone cement, improve the controlled degradation of composite.
Brief description of the drawings
Fig. 1 is the TEM figures of flexible ultra-fine sub- nano wire prepared by embodiment 1；
Fig. 2 is the TEM figures of flexible ultra-fine sub- nano wire prepared by embodiment 1；
Fig. 3 is the EDS figures of flexible superfine nanowire prepared by embodiment 1；
Fig. 4 is the infrared spectrogram for implementing flexible superfine nanowire prepared by Fig. 4.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified；Material used, reagent
Deng unless otherwise specified, commercially obtaining.
Embodiment 1
In 50mL beaker, 2mL oleic acid is added, then 6mL ethanol add 0.25M calcium nitrate 6mL, 0.15M's
Sodium radio-phosphate,P-32 solution 6mL and 0.25M europium nitrate 0.6mL, stir, and sealing of hole film seals beaker mouthful, quiet in 25 DEG C of insulating boxs
Put 7d.After reaction terminates, precipitation is collected by centrifugation, and is washed with hexamethylene and ethanol and obtains end-product for several times.
By transmission electron microscope detect display reaction product be sub-nano level superfine line, diameter about 0.7nm, length be 0.5 ~
5 μm, as depicted in figs. 1 and 2；Know that the sub- nanometer superfine wire of gained contains element calcium, phosphorus, europium through EDS analyses, as shown in Figure 3；Product
Infrared spectrogram show the infrared spectrum feature for meeting hydroxyapatite, as shown in Figure 4.
Embodiment 2
In 50mL beaker, 2mL oleic acid is added, then 6mL ethanol add 0.25M calcium nitrate 6mL, 0.15M's
Sodium radio-phosphate,P-32 solution 6mL and 0.25M terbium nitrate 0.6mL, stir, and sealing of hole film seals beaker mouthful, quiet in 10 DEG C of insulating boxs
Put 10d.After reaction terminates, precipitation is collected by centrifugation, and is washed with hexamethylene and ethanol and obtains end-product for several times.Acquired results and reality
Apply example 1 similar.
Embodiment 3
In 50mL beaker, 2mL oleic acid is added, then 6mL ethanol add 0.25M calcium nitrate 6mL, 0.15M's
Sodium radio-phosphate,P-32 solution 6mL and 0.25M neodymium nitrate 0.6mL, stir, and sealing of hole film seals beaker mouthful, are stood in 4 DEG C of refrigerators
15d.After reaction terminates, precipitation is collected by centrifugation, and is washed with hexamethylene and ethanol and obtains end-product for several times.Acquired results are with implementing
Example 1 is similar.
Embodiment 4
In 250mL beaker, 10mL oleic acid is added, then 30mL ethanol add 0.25M calcium nitrate 30mL,
0.15M sodium radio-phosphate,P-32 solution 30mL and 0.25M ytterbium nitrate 6mL, stir, and sealing of hole film seals beaker mouthful, in 25 DEG C of constant temperature
7d is stood in case.After reaction terminates, precipitation is collected by centrifugation, and is washed with hexamethylene and ethanol and obtains end-product for several times.Gained knot
It is really similar to Example 1.
Embodiment 5
In 250mL beaker, 10mL oleic acid is added, then 40mL ethanol add 0.25M calcium nitrate 30mL,
0.15M sodium radio-phosphate,P-32 solution 30mL and 0.25M erbium nitrate 3mL, stir, and sealing of hole film seals beaker mouthful, in 25 DEG C of constant temperature
7d is stood in case.After reaction terminates, precipitation is collected by centrifugation, and is washed with hexamethylene and ethanol and obtains end-product for several times.Gained knot
It is really similar to Example 1.
Claims (5)
1. a kind of preparation method of the sub- nano wire of flexible ultra-fine hydroxyapatite, it is characterised in that：In the mixing of oleic acid and ethanol
In solution, calcium saline solution, aqueous phosphatic and rare earth nitrate aqueous solution are added, makes the volume ratio of oleic acid, ethanol and water
For 1: (2~8):(2 ~ 8), stand 7 ~ 15 days at 0 DEG C~30 DEG C after stirring and obtain the sub- nanometer of flexible ultra-fine hydroxyapatite
Line, nanowire diameter is 0.6 ~ 0.8 nm, and length is 0.3 ~ 5 μm.
2. method according to claim 1, it is characterised in that：Calcium salt is calcium nitrate；Phosphate is selected from sodium phosphate, phosphoric acid hydrogen
Sodium, sodium dihydrogen phosphate；Calcium salt is 1 with phosphatic mol ratio:1.67.
3. method according to claim 1, it is characterised in that：Rare earth nitrades are the nitrate of trivalent rare earth, rare earth nitric acid
The mol ratio of salt and calcium salt is (0.05 ~ 0.2):1.
4. method according to claim 3, it is characterised in that：The rare earth nitrades be lanthanum nitrate, cerous nitrate, neodymium nitrate,
Gadolinium nitrate, europium nitrate, terbium nitrate, ytterbium nitrate.
5. method according to claim 1, it is characterised in that：The whole production obtained for several times using hexamethylene and ethanol cyclic washing
Thing, hexamethylene is detergent, and ethanol is to help precipitating reagent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111808390B (en) * | 2020-06-30 | 2022-11-08 | 扬州大学 | Hydroxyapatite nanowire/polytetrafluoroethylene composite and preparation method thereof |
| CN112675805B (en) * | 2021-01-25 | 2022-04-19 | 西北师范大学 | Preparation method of hydroxyapatite nanowire composite molybdenum disulfide adsorbent |
| CN113621387B (en) * | 2021-08-11 | 2022-10-25 | 清华大学 | Liquid crystal composite polarizing film and preparation method and application thereof |
| CN116270254B (en) * | 2022-11-28 | 2024-03-19 | 昆明理工大学 | Preparation method and application of amorphous calcium phosphate-cerium phosphate composite material |
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| CA2447333C (en) * | 2002-10-30 | 2006-05-23 | Les Technologies Elcotech Inc. | Process for the treatment of phosphatic water |
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| CN101723341A (en) * | 2009-11-06 | 2010-06-09 | 上海师范大学 | Preparation method of hydroxylapatite nano fibers or nano wires |
| CN102249205A (en) * | 2011-05-06 | 2011-11-23 | 清华大学 | Rare earth doped hydroxyfluorapatite monocrystal nanometer wire and preparation method thereof |
| CN102826526A (en) * | 2012-08-21 | 2012-12-19 | 西北大学 | Preparation method of carbonate hydroxylapatite ultrafine nano-wires |
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Patent Citations (5)
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| CA2447333C (en) * | 2002-10-30 | 2006-05-23 | Les Technologies Elcotech Inc. | Process for the treatment of phosphatic water |
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| CN101723341A (en) * | 2009-11-06 | 2010-06-09 | 上海师范大学 | Preparation method of hydroxylapatite nano fibers or nano wires |
| CN102249205A (en) * | 2011-05-06 | 2011-11-23 | 清华大学 | Rare earth doped hydroxyfluorapatite monocrystal nanometer wire and preparation method thereof |
| CN102826526A (en) * | 2012-08-21 | 2012-12-19 | 西北大学 | Preparation method of carbonate hydroxylapatite ultrafine nano-wires |
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