CN1958517A - Method for cladding Nano carbon tube by using hydroxyapatite - Google Patents
Method for cladding Nano carbon tube by using hydroxyapatite Download PDFInfo
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Abstract
This invention discloses a method for coating carbon nanotubes (CNTs) with hydroxyapatite. The method comprises: (1) refluxing CNTs in a strongly oxidative acid at 100-140 deg.C, then washing to neutrality, drying, and milling; (2) dispersing oxidized CNTs by ultrasonication with anionic surfactant as the dispersant to obtain 0.2-1 g/L suspension; (3) preparing Ca(NO3)2 solution and (NH4)2HPO4 solution; (4) slowly adding Ca(NO3)2 solution into the suspension, adjusting the pH value to 10-13 with ammonia solution, dispersing by ultrasonication, and transferring into a reactor; (5) slowly adding (NH4)2HPO4 solution into the reactor at a (NH4)2HPO4/ Ca(NO3)2 mol ratio of 3:5, aging at 10-80 deg.C, washing the precipitate and drying to obtain the product. The method is easy to operate and can realize intimate bonding of CNTs and hydroxyapatite.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube of surface modification, relate in particular to a kind of method, belong to technical field of biological material with the hydroxyapatite enveloped carbon nanometer tube.
Background technology
Carbon nanotube has unique metal or semi-conductive electroconductibility, extremely strong physical strength, toughness, bigger specific surface area (120～300m
2/ g), better adsorption capability, catalysis characteristics and stronger microwave absorption capacity and unique vestibule structure, can be widely used in various high-tech technical fields, be a kind of new-type functional material and structured material.
At present, at biomedical sector, the application of carbon nanotube is mainly concentrated both ways: the one, and utilize on its structure specific surface area big, the characteristics that can carry high amount of drug are as pharmaceutical carrier; The 2nd, utilize its high Young's modulus and Young's modulus to strengthen pottery and polymer-based carbon biomaterial.But early-stage Study shows that carbon nanotube deposits easily, and is unfavorable to health in lung, stomach, kidney and the bone of animal.
On the other hand, the raising of composite property and carbon nanotube in matrix dispersion and to combine situation closely related at the interface.In order to improve the surface tissue of carbon nanotube, generally adopt surface modification method, with improve or change the dispersed of carbon nanotube and and other materials between consistency.
Hydroxyapatite is that the main component, particularly nano level needle-like phosphatic rock of formation people bone mineral is that component, form or degree of crystallinity all more approach people's bone, thereby has natural affinity and show biological activity with natural bone.Be characterized in that fragility is big, easy fracture.Adopting high-strength second phase material and hydroxyapatite compound, is to improve one of modal method of its mechanical property.
Studies show that: utilize the hydroxyapatite enveloped carbon nanometer tube can effectively suppress the toxicity of carbon nanotube, and, through coated carbon nanotube can with hydroxy apatite powder with any than mixing, and the interface is in conjunction with stronger between the two, effective transmitted load, and then the strength and toughness of raising hydroxyapatite, be a kind of very promising bio-medical material, aspect pharmaceutical carrier, have broad application prospects.
Summary of the invention
At the demand in the deficiencies in the prior art and different application field, the object of the present invention is to provide a kind of method with the hydroxyapatite enveloped carbon nanometer tube.
The inventive method is simple to operate, and is convenient, and realized combining closely of hydroxyapatite and carbon nanotube, and almost all carbon nanotube is coated by hydroxyapatite, is the effective way of preparation hydroxyapatite enveloped carbon nanometer tube.
The method of the invention is achieved through the following technical solutions:
With strong oxidizing property acid treatment carbon nanotube, make its surface produce active group, add anion surfactant then, utilize negatively charged ion and Ca (NO
3)
2Charge attraction effect in the solution between the calcium ion is adsorbed in carbon nano tube surface with the calcium original position, along with (NH
4)
2HPO
4The adding of solution, original position generates the hydroxylapatite/carbon nanotube powder.
Method with the hydroxyapatite enveloped carbon nanometer tube of the present invention is specifically finished by following steps:
1) with carbon nanotube in acid with strong oxidizing property, in 100 ℃～140 ℃ condition reflow treatment 1～6 hour, be washed with distilled water to neutrality then, oven dry, grind, cross behind 300 mesh sieves standby;
2) with the anion surfactant be dispersion agent, distilled water is dispersion medium, and the carbon nanotube that step 1) is made adds wherein, ultra-sonic dispersion 0.5～3 hour, and be mixed with the suspension that concentration is 0.2～1g/L;
3) respectively with Ca (NO
3)
2With (NH
4)
2HPO
4Being mixed with ionic calcium soln and the concentration that concentration is 0.4～3mol/L is the phosphate ion solution of 0.24～1.8mol/L;
4) Ca (NO that step 3) is made
3)
2Solution slowly adds step 2) in the described suspension, regulating the pH value with ammoniacal liquor is 10～13, ultra-sonic dispersion is 0.5～1 hour again, changes in the reaction vessel then;
5) (the NH that step 3) is made
4)
2HPO
4Solution is by (NH
4)
2HPO
4With Ca (NO
3)
2Mol ratio is 3: 5 a ratio, under constantly stirring, splashes in the described reaction vessel of step 4) with separating funnel, and in 10～80 ℃ of condition ageings processing 1～5 day, the gained precipitation is used distilled water wash, after 80 ℃ of vacuum-drying, promptly obtains the hydroxyapatite coated carbon nanotube.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, used carbon nanotube is preferably the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over or the preparation of laser evaporation method in the step 1).
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, the acid with strong oxidizing property described in the step 1) is preferably the mixed solution of concentrated nitric acid, the vitriol oil or concentrated nitric acid and any ratio of the vitriol oil.
Wherein: above-mentioned acid with strong oxidizing property most preferably is concentrated nitric acid.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, preferably 110 ℃～130 ℃ of the reflow treatment temperature described in the step 1), preferably 3～5 hours reflow treatment time.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, step 2) anion surfactant described in is one of citric acid, cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyacrylic acid, and the weight percent concentration of use is 1～4%.
Wherein, above-mentioned anion surfactant is preferably one of citric acid, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, (the NO of Ca described in the step 3)
3)
2Strength of solution is to be preferably 0.8～2.3mol/L, (NH
4)
2HPO
4Strength of solution is preferably 0.5～1.5mol/L.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, the value of pH described in the step 4) is preferably 10～12.
In the above-mentioned method with the hydroxyapatite enveloped carbon nanometer tube, the treatment temp of ageing described in the step 5) is preferably 25～60 ℃, and the ageing treatment time is preferably 1～3 day.
Wherein, above-mentioned ageing treatment temp most preferably is 25～45 ℃, and the ageing treatment time most preferably is 1～2 day.
Method with the hydroxyapatite enveloped carbon nanometer tube of the present invention has the following advantages:
(1) the acid with strong oxidizing property reflow treatment can be removed impurity under the prerequisite of destroying carbon nanometer tube structure not, and introduces functional group at port and sidewall, realizes the carboxylic acidization of carbon nanotube.
(2) be auxiliary with anion surfactant, finish the functionalization of carbon nanotube, introduce active group, make it in the water soluble on its surface.
(3) by electrostatic interaction between reactive ion and the active group and the ionic linkage effect between the reactive ion, the nanometer hydroxyapatite in-situ deposition, cover carbon nano tube surface thick and fast, form than strong interfacial bond with it.
Method with the hydroxyapatite enveloped carbon nanometer tube of the present invention, simple, convenient, and realized combining closely of hydroxyapatite and carbon nanotube, test result shows: almost all carbon nanotube is coated by hydroxyapatite, reduce greatly through coated carbon nanotube toxicity, can safety as pharmaceutical carrier; In addition, the carbon pipe after coating can with hydroxyapatite with any than mixing, be expected to improve greatly the mechanical property of material, aspect human loaded bone, have application potential.
Description of drawings
The X ray diffracting spectrum of Fig. 1 hydroxyapatite enveloped carbon nanometer tube
The transmission electron microscope photo of Fig. 2 hydroxyapatite enveloped carbon nanometer tube
Embodiment
With the indefiniteness experiment the method and the effect with the hydroxyapatite enveloped carbon nanometer tube of invention are further illustrated below.
Embodiment 1
1) with multi-walled carbon nano-tubes in concentration is 70% concentrated nitric acid, in 120 ℃ of condition reflow treatment 4 hours, be washed with distilled water to neutrality then, oven dry, grind, cross behind 300 mesh sieves standby;
2) be dispersion agent with the anion surfactant sodium laurylsulfonate, distilled water is dispersion medium, is made into mass percent and is 1% sodium dodecyl sulfate solution, and the carbon nanotube that step 1) is made adds wherein, ultra-sonic dispersion 2 hours, and be mixed with the suspension that concentration is 0.6g/L;
3) respectively with Ca (NO
3)
2With (NH
4)
2HPO
4Being mixed with ionic calcium soln and the concentration that concentration is 1.2mol/L is the phosphate ion solution of 0.72mol/L;
4) Ca (NO that step 3) is made
3)
2Solution slowly adds step 2) in the described suspension, regulating the pH value with ammoniacal liquor is 10, ultra-sonic dispersion is 0.5 hour again, changes in the reaction vessel then;
5) (the NH that step 3) is made
4)
2HPO
4Solution is by (NH
4)
2HPO
4With Ca (NO
3)
2Mol ratio is 3: 5 a ratio, under constantly stirring, splashes in the described reaction vessel of step 4) with separating funnel, and in 25 ℃ of condition ageings processing 1 day, the gained precipitation is used distilled water wash, after 20 hours, promptly obtains the hydroxyapatite coated carbon nanotube through 80 ℃ of vacuum-dryings.
Fig. 1 is the X-ray diffractogram of hydroxyapatite enveloped carbon nanometer tube in the present embodiment, and diffraction peak the diffraction peak of any impurity do not occur corresponding to the crystal face diffraction of hydroxyapatite in the spectrogram, illustrates that hydroxyapatite is a crystal form and purer; Because the characteristic peak of carbon nanotube overlaps with the diffraction peak of hydroxyapatite, and the diffraction peak intensity of HAp is very high, so can not go out the diffraction peak of carbon nanotube in the composite granule respectively.As can be seen from Figure 2, hydroxyapatite crystal grain closely covers carbon nano tube surface, and crystal grain diameter is about 20nm.
Embodiment 2
1) with the multi-walled carbon nano-tubes of catalystic pyrolysis preparation in concentration is 98.3% sulfuric acid, in 100 ℃ of condition reflow treatment 1 hour, be washed with distilled water to neutrality then, oven dry, grind, cross behind 300 mesh sieves standby;
2) with the anionic surfactant sodium dodecylbenzene sulfonate be dispersion agent, distilled water is dispersion medium, is made into mass percent and is 1% Sodium dodecylbenzene sulfonate solution, and the carbon nanotube that step 1) is made adds wherein, ultra-sonic dispersion 3 hours, and be mixed with the suspension that concentration is 1g/L;
3) respectively with Ca (NO
3)
2With (NH
4)
2HPO
4Being mixed with ionic calcium soln and the concentration that concentration is 1.2mol/L is the phosphate ion solution of 0.72mol/L;
4) Ca (NO that step 3) is made
3)
2Solution slowly adds step 2) in the described suspension, regulating the pH value with ammoniacal liquor is 13, ultra-sonic dispersion is 1 hour again, changes in the reaction vessel then;
5) (the NH that step 3) is made
4)
2HPO
4Solution is by (NH
4)
2HPO
4With Ca (NO
3)
2Mol ratio is 3: 5 a ratio, under constantly stirring, splashes in the described reaction vessel of step 4) with separating funnel, and in 80 ℃ of condition ageings processing 1 day, the gained precipitation is used distilled water wash, after 18 hours, promptly obtains the hydroxyapatite coated carbon nanotube through 80 ℃ of vacuum-dryings.
Embodiment 3
1) multi-walled carbon nano-tubes (V in the mixed solution of the concentrated nitric acid and the vitriol oil that the laser evaporation method is prepared
Sulfuric acid/ V
Nitric acid=3: 1),, be washed with distilled water to neutrality then in 140 ℃ of condition reflow treatment 6 hours, oven dry, grind, cross behind 300 mesh sieves standby;
2) be dispersion agent with the anion surfactant citric acid, distilled water is dispersion medium, is made into mass percent and is 2% citric acid solution, and the carbon nanotube that step 1) is made adds wherein, ultra-sonic dispersion 0.5 hour, and be mixed with the suspension that concentration is 0.3g/L;
3) respectively with Ca (NO
3)
2With (NH
4)
2HPO
4Being mixed with ionic calcium soln and the concentration that concentration is 1.2mol/L is the phosphate ion solution of 0.72mol/L;
4) Ca (NO that step 3) is made
3)
2Solution slowly adds step 2) in the described suspension, regulating the pH value with ammoniacal liquor is 11, ultra-sonic dispersion is 0.5 hour again, changes in the reaction vessel then;
5) (the NH that step 3) is made
4)
2HPO
4Solution is by (NH
4)
2HPO
4With Ca (NO
3)
2Mol ratio is 3: 5 a ratio, under constantly stirring, splashes in the described reaction vessel of step 4) with separating funnel, and in 15 ℃ of condition ageings processing 5 days, the gained precipitation is used distilled water wash, after 25 hours, promptly obtains the hydroxyapatite coated carbon nanotube through 80 ℃ of vacuum-dryings.
Claims (10)
1. method with the hydroxyapatite enveloped carbon nanometer tube, finish by following steps:
1) with carbon nanotube in acid with strong oxidizing property, in 100 ℃～140 ℃ condition reflow treatment 1～6 hour, be washed with distilled water to neutrality then, oven dry, grind, cross behind 300 mesh sieves standby;
2) with the anion surfactant be dispersion agent, distilled water is dispersion medium, and the carbon nanotube that step 1) is made adds wherein, ultra-sonic dispersion 0.5～3 hour, and be mixed with the suspension that concentration is 0.2～1g/L;
3) respectively with Ca (NO
3)
2With (NH
4)
2HPO
4Being mixed with ionic calcium soln and the concentration that concentration is 0.4～3mol/L is the phosphate ion solution of 0.24～1.8mol/L;
4) Ca (NO that step 3) is made
3)
2Solution slowly adds step 2) in the described suspension, regulating the pH value with ammoniacal liquor is 10～13, ultra-sonic dispersion is 0.5～1 hour again, changes in the reaction vessel then;
5) (the NH that step 3) is made
4)
2HPO
4Solution is by (NH
4)
2HPO
4With Ca (NO
3)
2Mol ratio is 3: 5 a ratio, under constantly stirring, splashes in the described reaction vessel of step 4) with separating funnel, and in 10～80 ℃ of condition ageings processing 1～5 day, the gained precipitation is used distilled water wash, after 80 ℃ of vacuum-drying, promptly obtains the hydroxyapatite coated carbon nanotube.
2. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, used carbon nanotube is the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over or the preparation of laser evaporation method in the step 1).
3. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, the acid with strong oxidizing property described in the step 1) is the mixed solution of concentrated nitric acid, the vitriol oil or concentrated nitric acid and any ratio of the vitriol oil.
4. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, the reflow treatment temperature described in the step 1) is 110 ℃～130 ℃, and the reflow treatment time is 3～5 hours.
5. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1, it is characterized in that, step 2) anion surfactant described in is one of citric acid, cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyacrylic acid, and the weight percent concentration of use is 1～4%.
6. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 5 is characterized in that step 2) described in anion surfactant be one of citric acid, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate.
7. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, (the NO of Ca described in the step 3)
3)
2Strength of solution is 0.8～2.3mol/L, (NH
4)
2HPO
4Strength of solution is 0.5～1.5mol/L.
8. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, the value of pH described in the step 4) is 10～12.
9. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 1 is characterized in that, the treatment temp of ageing described in the step 5) is 25～60 ℃, and the ageing treatment time is 1～3 day.
10. the method with the hydroxyapatite enveloped carbon nanometer tube according to claim 9 is characterized in that, the treatment temp of ageing described in the step 5) is 25～45 ℃, and the ageing treatment time is 1～2 day.
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| CN102328922A (en) * | 2010-07-14 | 2012-01-25 | 天津工业大学 | Preparation method of nano hydroxyapatite |
| CN101773682B (en) * | 2009-11-20 | 2013-01-16 | 湖北工业大学 | Method for preparing polymer three-dimensional porous scaffold |
| CN105098154A (en) * | 2015-07-09 | 2015-11-25 | 天津工业大学 | Preparation method for anode material of red phosphorous cladding carbon nano tube composite ion battery |
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| CN108796572A (en) * | 2018-06-27 | 2018-11-13 | 陕西科技大学 | A method of hydroxyapatite coating layer is prepared in carbon nano tube surface based on electrochemical deposition method compound bio mineralising method |
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| CN1172873C (en) * | 2003-04-02 | 2004-10-27 | 山东大学 | Composite hydroxyapatite/carbon nanotube material and its prepn process |
| CN100436307C (en) * | 2003-11-07 | 2008-11-26 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite / carbon nanometer tube nanometer compound powder body and in-situ synthetic method |
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| CN102328922A (en) * | 2010-07-14 | 2012-01-25 | 天津工业大学 | Preparation method of nano hydroxyapatite |
| CN105098154A (en) * | 2015-07-09 | 2015-11-25 | 天津工业大学 | Preparation method for anode material of red phosphorous cladding carbon nano tube composite ion battery |
| CN105289578A (en) * | 2015-11-24 | 2016-02-03 | 华南理工大学 | Metal oxide/carbon nanotube composite photocatalyst, and preparation method and application thereof |
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| CN108796572A (en) * | 2018-06-27 | 2018-11-13 | 陕西科技大学 | A method of hydroxyapatite coating layer is prepared in carbon nano tube surface based on electrochemical deposition method compound bio mineralising method |
| CN108796572B (en) * | 2018-06-27 | 2020-06-09 | 陕西科技大学 | Method for preparing hydroxyapatite coating on surface of carbon nanotube based on electrochemical deposition method and composite biomineralization method |
| CN115006589A (en) * | 2022-06-28 | 2022-09-06 | 奥精医疗科技股份有限公司 | Carbon nanotube modified mineralized collagen material and preparation method and application thereof |
| CN115120774A (en) * | 2022-06-28 | 2022-09-30 | 奥精医疗科技股份有限公司 | Carbon nano tube strengthened mineralized collagen material and preparation method and application thereof |
| CN115120774B (en) * | 2022-06-28 | 2024-05-28 | 奥精医疗科技股份有限公司 | Carbon nano tube reinforced mineralized collagen material and preparation method and application thereof |
| CN117735869A (en) * | 2024-02-21 | 2024-03-22 | 北京安科兴业科技股份有限公司 | Carbon nano tube reinforced magnesium silicate cementing material and preparation method thereof |
| CN117735869B (en) * | 2024-02-21 | 2024-05-28 | 北京安科兴业科技股份有限公司 | Carbon nano tube reinforced magnesium silicate cementing material and preparation method thereof |
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