CN1541935A - Hydroxyapatite / carbon nanometer tube nanometer compound powder body and in-situ synthetic method - Google Patents
Hydroxyapatite / carbon nanometer tube nanometer compound powder body and in-situ synthetic method Download PDFInfo
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- CN1541935A CN1541935A CNA200310108523XA CN200310108523A CN1541935A CN 1541935 A CN1541935 A CN 1541935A CN A200310108523X A CNA200310108523X A CN A200310108523XA CN 200310108523 A CN200310108523 A CN 200310108523A CN 1541935 A CN1541935 A CN 1541935A
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Abstract
The present invention provides one simple process of in-situ synthesizing composite hydroxyapatite/carbon nanotube powder. The process features that polyvinyl imine or dodecyl sodium sulfate is used as dispersant in introducing active NH2+ and SO4- radical into the surface of carbon nanotube without altering the structure of carbon nanotube. Then, ammonium hydrogen phasphate and calcium nitrate are used as material to synthesize hydroxyapatite, and the electrostatic effect of reaction ion and active radical and the ion bond effect of the reaction ions are utilized to deposit amorphous hydroxyapatite on the surface of carbon nanotube. The deposit is shifted to high pressure reactor for hydrothermal reaction to obtain composite carbon nanotube powder covered closely with hydroxyapatite crystal particles of 20-25 nm size. The present invention provides one effective way of developing high performance composite carbon nanotube material.
Description
Technical field
The invention relates to a kind of hydroxylapatite/carbon nanotube composite nano-powder and preparation method, belong to field of nanocomposite materials with tight interfacial combined function.
Technical background
Hydroxyapatite is that the essential mineral of body bone tissue and tooth is formed, all excellent biological compatibility is arranged with human body hard tissue and skin, muscle tissue etc. and become that modern age, biomedical engineering field was generally acknowledged for bone material.Because the mechanical property of hydroxyapatite sintered compact is relatively poor, bending strength is between 100-160Mpa, and fracture toughness property is 0.5-1.0Mpam only, and this has limited the application of hydroxylapatite ceramic to a great extent.It is compound to adopt second phase material of high-strength, high tenacity and hydroxyapatite to carry out, and is to improve one of the most frequently used method of its mechanical property.Carbon is a kind of bio-inert material, and chemical stability is good in the human body environment, nontoxicity, and no rejection has excellent biological compatibility.Though carbon can not form the direct chemical bonding with human normal tissue, have and bring out and promotion is organized in its epontic effect.Carbon nanotube has nano level caliber, high intensity and great toughness, its length-to-diameter ratio is very high, can not destroy the continuity of matrix at compound tense, be ideal material (F.H.Gojny, the J.Nastalczyk as the matrix material strengthening phase, Z.Roslaniec, K.Schulte.Chem Phys Lett, Vol.370 (2003), pp.820).
The interface of carbon nanotube and matrix is one of most important link in the nanometer tube composite materials research.In the process of development nanometer tube composite materials, this research can guarantee in the nanometer tube composite materials structure that nanotube follows a good stress transfer is arranged between matrix.Oxidizer treatment carbon nanotubes such as nitration mixture are at tube wall surface introducing-COOH, and-OH behind the groups such as-C=O, can effectively strengthen the bonding force of carbon nanotube and matrix.But studies show that the carbon nanotube Young's modulus of oxide treatment can reduce greatly, the composite material toughness that makes also decrease (M.J.Treacy, T.W.Ebbesen, J.M.Gibson, Nature, Vol.381 (1996), pp.678.).Carbon nanotube effectively combines but with basal body interface and can the structure of carbon nanotube not damaged, and is the key factor that makes the premium properties carbon nano tube compound material.Carbon nanotube is made up of single carbon atom, do not have reactive bond and group, water insoluble again and organic solvent is so carry out relatively difficulty (T.Seeger of chemically modified to it, Th.K hler, Th.Frauenheim, N.Grobert, M.R ü hle, M.Terrones, G.Seifert, Chem.Commun. (2002), pp.34).How by finishing, improve the interface bond strength of hydroxyapatite and carbon nanotube, thereby the comprehensive mechanical property of raising hydroxyapatite then is that people thirst for the problem that solves for a long time.By the ion dispersion agent introduce active group in carbon nano tube surface, in-situ deposition prepares the hydroxyapatite nano composite granule, is the effective way that addresses this problem.
Summary of the invention
The object of the present invention is to provide a kind of hydroxylapatite/carbon nanotube composite nano-powder and in-situ synthetic method with tight interfacial combined function.The present invention introduces active group and can not change the structure of carbon nanotube in carbon nano tube surface by the ion dispersion agent, the hydroxyapatite in-situ deposition, covers carbon nano tube surface thick and fast.The method that is provided is simple, and is easy to operate, and polymine or sodium lauryl sulphate dispersant adsorption are introduced active group-NH after carbon nano tube surface
2 +,-SO
4 -, utilizing the electrostatic interaction of reactive ion and active group and the ionic linkage effect between the reactive ion, hydroxyapatite in-situ is deposited on carbon nano tube surface.Carbon nanotube combines with the hydroxyapatite matrix is effective.
Hydroxylapatite/carbon nanotube composite nano-powder provided by the invention has two kinds:
(1) amorphous hydroxyapatite in-situ deposits, covers thick and fast carbon nano tube surface;
(2) hydroxyapatite crystal grain closely covers the composite nano-powder of carbon nano tube surface, and hydroxyapatite crystal grain diameter is 20-25nm.
Characteristics of the present invention are: successfully introducing active group with dispersion agent in carbon nano tube surface, is raw material with Secondary ammonium phosphate, nitrocalcite, and deionized water is a solvent, strong aqua regulator solution pH value.By the electrostatic interaction of reactive ion and active group and the ionic linkage effect between the reactive ion, amorphous hydroxyapatite in-situ deposits, covers thick and fast carbon nano tube surface.Precipitation moved to carry out hydrothermal treatment consists in the autoclave, can obtain the carbon nano-tube composite powder that hydroxyapatite crystal grain closely covers.
Concrete steps are:
(1) carbon nanotube is joined in polymine or the sodium lauryl sulphate dilute solution, ultra-sonic dispersion 0.5-2 hour, make carbon nano tube surface introducing-NH
2 +,-SO
4 -Active group carries out finishing.
(2) modified carbon nanotube suspension is joined Secondary ammonium phosphate or calcium nitrate aqueous solution, ultrasonic 5-15 minute.
(3) nitrocalcite or ammonium dibasic phosphate aqueous solution slowly are added drop-wise to above-mentioned mixing solutions, under the agitator vigorous stirring, generate precipitation.Described mixing speed 400-1000 rev/min, 0 ℃-25 ℃ of temperature of reaction, reaction times 1-10 hour, the pH value was greater than 10.
(4) partly precipitated washing, alcohol are washed for several times, dry, grinding obtains carbon nanotube/amorphous hydroxyapatite composite powder.
(5) will remain precipitation and change in the autoclave, sealing to autoclave volumetrical 50-90%.
(6) autoclave is put into baking oven 120-200 ℃ of insulation 8-20 hour.
(7) after autoclave naturally cools to room temperature, take out product, washing, alcohol are washed, and dry, grinding obtains the carbon nano-tube composite powder that hydroxyapatite crystal grain closely covers.Hydroxyapatite crystal grain diameter is about 20-25nm.Reaction principle is: (a) polymine modified carbon nanotube suspension is joined in the ammonium dibasic phosphate aqueous solution PO
4 3-By electrostatic interaction and-NH
2 +-combination.Calcium nitrate aqueous solution is joined in this mixing solutions, under the alkaline condition of pH＞10, Ca
2+PO with carbon nano tube surface absorption
4 3-By ionic linkage in conjunction with forming amorphous hydroxyapatite layer; And then precipitation moved to carry out hydrothermal treatment consists in the autoclave, obtaining the tight coated carbon nanotube composite granule of hydroxyapatite crystal grain, hydroxyapatite crystal grain diameter is about 25nm; (b) sodium lauryl sulphate modified carbon nanotube suspension is joined in the calcium nitrate aqueous solution Ca
2+By electrostatic interaction and-SO
4 -In conjunction with.Ammonium dibasic phosphate aqueous solution is joined in the above-mentioned mixing solutions, under the alkaline condition of pH＞10, PO
4 3-Ca with carbon nano tube surface absorption
2+By ionic linkage in conjunction with forming amorphous hydroxyapatite layer; Precipitation moved to carry out hydrothermal treatment consists in the autoclave, obtain the tight coated carbon nanotube composite granule of hydroxyapatite crystal grain, hydroxyapatite crystal grain diameter is about 20nm.
The characteristics of hydroxylapatite/carbon nanotube nano composite powder preparation provided by the invention are:
(1) successfully introducing active group with dispersion agent in carbon nano tube surface and can not change the structure of carbon nanotube, combines closely in the composite granule hydroxyapatite matrix crystal grain and the carbon nanotube interface of preparation.By the electrostatic interaction of reactive ion and active group and the ionic linkage effect between the reactive ion, amorphous hydroxyapatite in-situ deposits, covers thick and fast carbon nano tube surface.In 120-200 ℃ of hydro-thermal reaction 8-20h, hydroxylapatite crystal is complete at described hydrothermal temperature, and crystal grain diameter is about 20-25nm.
(2) preparation method is simply effective, has versatility.The positive and negative reactive ion for preparing other ceramic matrix raw material replaces the positive and negative reactive ion of preparation hydroxyapatite raw material, can prepare the matrix material of other ceramic matrixs and carbon nanotube.
Description of drawings
The X-ray diffraction spectrogram of Fig. 1 carbon nanometer tube/hydroxyapatite composite granule
(a) hydrothermal treatment consists not, (b) hydrothermal treatment consists is 20 hours
Fig. 2 is the electronic spectrum of hydroxyapatite in the composite granule of hydrothermal treatment consists not
20 hours composite granule transmission electron microscope photo of Fig. 3 hydrothermal treatment consists
Fig. 4 is the composite granule transmission electron microscope photo of hydrothermal treatment consists not
Patent working
Further specify embodiment and effect with following indefiniteness embodiment:
Embodiment 1
Carbon nanotube is added the 1wt% sodium dodecyl sulfate solution, and ultra-sonic dispersion joins the 0.01M calcium nitrate aqueous solution after 1 hour, ultrasonic 10 minutes.The 0.02M ammonium dibasic phosphate aqueous solution slowly is added drop-wise to the above-mentioned mixing solutions of 500 rev/mins of stirrings, and reaction generated precipitation in 2 hours under the ice-water bath condition.Partly precipitated washing, alcohol are washed for several times, and dry, grinding obtains carbon nanotube/unformed hydroxyapatite composite powder.To remain precipitation and change in the autoclave, sealing to autoclave volumetrical 80%.Autoclave is put into baking oven, 120 ℃ of insulations 20 hours.After autoclave naturally cools to room temperature, take out product, washing, alcohol are washed, and dry, grinding obtains the carbon nano-tube composite powder that hydroxyapatite crystal grain closely covers.Fig. 1 is the X-ray diffraction spectrogram of the carbon nanometer tube/hydroxyapatite composite granule of present embodiment preparation.The diffraction peak of not having only carbon nanotube in the composite granule of hydrothermal treatment consists illustrates that hydroxyapatite is an amorphous state, the existence of photoelectron spectrum (Fig. 2) display element Ca, P, O.After the hydrothermal treatment consists 20 hours, diffraction peak is not found the diffraction peak of any impurity corresponding to the crystal face diffraction of hydroxyapatite in the spectrogram, illustrates that hydroxyapatite is a crystal form and purer; Fig. 3 is the composite granule electromicroscopic photograph of hydrothermal treatment consists 20h, and hydroxyapatite crystal grain closely covers carbon nano tube surface, and hydroxyapatite crystal grain diameter is about 20nm.
Embodiment 2
Carbon nanotube is added 1wt% polymine dilute solution, and ultra-sonic dispersion joins the 0.02M ammonium dibasic phosphate aqueous solution after 1 hour, ultrasonic 10 minutes.The 0.01M calcium nitrate aqueous solution slowly is added drop-wise to the above-mentioned mixing solutions of 500 rev/mins of stirrings, and reaction generated precipitation in 2 hours under the ice-water bath condition.Precipitation is changed in the autoclave to autoclave volumetrical 80% over to sealing.Autoclave is put into baking oven, 120 ℃ of insulations 8 hours.After autoclave naturally cools to room temperature, take out product, washing, alcohol are washed, and dry, grinding obtains the carbon nano-tube composite powder that hydroxyapatite crystal grain closely covers.Fig. 4 is the transmission electron microscope photo of the carbon nanometer tube/hydroxyapatite composite granule of the not hydrothermal treatment consists of present embodiment preparation, hydroxyapatite layer presents transparent body of paste and is distributed in carbon nano tube surface under the electron beam irradiation, illustrate that hydroxyapatite is a unformed shape.
Claims (10)
1. the hydroxylapatite/carbon nanotube composite nano-powder is characterized in that amorphous hydroxyapatite in-situ deposits, covers thick and fast the surface of carbon nanotube.
2. press the in-situ synthetic method of the described hydroxylapatite/carbon nanotube composite nano-powder of claim 1, it is characterized in that: adopt yin, yang ion dispersion agent to introduce active group in carbon nano tube surface, with Secondary ammonium phosphate, nitrocalcite is raw material, deionized water is a solvent, strong aqua regulator solution pH value; By the electrostatic interaction of reactive ion and active group and the ionic linkage effect between the reactive ion, unformed hydroxyapatite in-situ deposits, covers thick and fast carbon nano tube surface.
3. press the in-situ synthetic method of the described hydroxylapatite/carbon nanotube composite nano-powder of claim 2, it is characterized in that: yin, yang ion dispersion agent is respectively polymine and sodium lauryl sulphate, carbon nanotube ultrasonic time in dispersant solution is 0.5-2 hour, at carbon nano tube surface introducing-NH
2 +With-SO
4 -Active group.
4. by the in-situ synthetic method of claim 2 or 3 described hydroxylapatite/carbon nanotube composite nano-powders, it is characterized in that: (1) joins in the ammonium dibasic phosphate aqueous solution PO with polymine modified carbon nanotube suspension
4 3-By electrostatic interaction and-NH
2 +-combination.Calcium nitrate aqueous solution is joined in this mixing solutions, under the alkaline condition of pH＞10, Ca
2+PO with carbon nano tube surface absorption
4 3-By ionic linkage in conjunction with forming amorphous hydroxyapatite layer; Or (2) join in the calcium nitrate aqueous solution Ca with sodium lauryl sulphate modified carbon nanotube suspension
2+By electrostatic interaction and-SO
4 -In conjunction with, ammonium dibasic phosphate aqueous solution is joined in the above-mentioned mixing solutions, under the alkaline condition of pH＞10, PO
4 3-Ca with carbon nano tube surface absorption
2+By ionic linkage in conjunction with forming amorphous hydroxyapatite layer.
5. by the described hydroxylapatite/carbon nanotube composite nano-powder of claim 2 in-situ synthetic method, it is characterized in that original position synthetic condition is: be reflected at 0 ℃ of ice-water bath to 25 and ℃ carry out, the reaction times is 1-10 hour.
6. the hydroxylapatite/carbon nanotube composite nano-powder is characterized in that hydroxyapatite crystal grain closely covers the composite nano-powder of carbon nano tube surface, and hydroxyapatite crystal grain diameter is 20-25nm.
7. press the in-situ synthetic method of the described hydroxylapatite/carbon nanotube composite nano-powder of claim 6, it is characterized in that: adopt yin, yang ion dispersion agent to introduce active group in carbon nano tube surface, with Secondary ammonium phosphate, nitrocalcite is raw material, deionized water is a solvent, strong aqua regulator solution pH value; By the electrostatic interaction of reactive ion and active group and the ionic linkage effect between the reactive ion, in-situ deposition synthesizes unformed hydroxyapatite, and hydro-thermal reaction generates crystalline hydroxy phosphatic rock then, covers carbon nano tube surface thick and fast.
8. press the in-situ synthetic method of the described hydroxylapatite/carbon nanotube composite nano-powder of claim 7, it is characterized in that: yin, yang ion dispersion agent is respectively polymine and sodium lauryl sulphate, carbon nanotube ultrasonic time in dispersant solution is 0.5-2 hour, at carbon nano tube surface introducing-NH
2 +With-SO
4 -Active group.
9. by the in-situ synthetic method of claim 6 or 7 described hydroxylapatite/carbon nanotube composite nano-powders, it is characterized in that: (1) joins in the ammonium dibasic phosphate aqueous solution PO with polymine modified carbon nanotube suspension
4 3-By electrostatic interaction and-NH
2 +-combination.Calcium nitrate aqueous solution is joined in this mixing solutions, under the alkaline condition of pH＞10, Ca
2+PO with carbon nano tube surface absorption
4 3-By ionic linkage in conjunction with forming amorphous hydroxyapatite layer; And then precipitation moved to carry out hydrothermal treatment consists in the autoclave, obtaining the tight coated carbon nanotube composite granule of hydroxyapatite crystal grain, hydroxyapatite crystal grain diameter is about 25nm; Or (2) join in the calcium nitrate aqueous solution Ca with sodium lauryl sulphate modified carbon nanotube suspension
2+By electrostatic interaction and-SO
4 -In conjunction with, ammonium dibasic phosphate aqueous solution is joined in the above-mentioned mixing solutions, under the alkaline condition of pH＞10, PO
4 3-Ca with carbon nano tube surface absorption
2+By ionic linkage in conjunction with forming amorphous hydroxyapatite layer; Precipitation moved to carry out hydrothermal treatment consists in the autoclave, obtain the tight coated carbon nanotube composite granule of hydroxyapatite crystal grain, hydroxyapatite crystal grain diameter is about 20nm.
10. by the in-situ synthetic method of the described hydroxylapatite/carbon nanotube composite nano-powder of claim 6, it is characterized in that original position synthetic condition is: be reflected at 0 ℃ of ice-water bath to 25 and ℃ carry out, the reaction times is 1-10 hour; Hydrothermal temperature is 120-200 ℃, and the time is 8-20h.
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| CN100371243C (en) * | 2006-03-03 | 2008-02-27 | 中国科学院上海硅酸盐研究所 | Composite powder of nanomer tin dioxide particle in-situ coated carbon nanotube and its prepn process |
| CN100384782C (en) * | 2006-10-17 | 2008-04-30 | 山东大学 | Method for cladding Nano carbon tube by using hydroxyapatite |
| CN101491699B (en) * | 2009-03-03 | 2011-09-14 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced bone-cement biological composite material |
| CN101491696B (en) * | 2009-03-03 | 2011-09-14 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced hydroxylapatite composite material |
| CN102471049A (en) * | 2009-06-30 | 2012-05-23 | 韩华石油化学株式会社 | Blending improvement carbon-composite having carbon-nanotube and its continuous manufacturing method and apparatus |
| CN102502556A (en) * | 2011-12-14 | 2012-06-20 | 江南大学 | Method for preparing nano hydroxyapatite |
| CN104998301A (en) * | 2015-08-12 | 2015-10-28 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
| CN106835847A (en) * | 2017-03-13 | 2017-06-13 | 南昌大学 | A kind of preparation method of bio-compatibility carbon nanometer tube/hydroxyapatite extrusion coating paper |
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| CA2475110C (en) * | 2002-02-05 | 2010-03-23 | Cambridge Scientific, Inc. | Bioresorbable osteoconductive compositions for bone regeneration |
| CN1175911C (en) * | 2002-05-10 | 2004-11-17 | 清华大学 | Nano carbon tube reinforced plastics/ceramics-base composition for repairing bone |
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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 |
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| CN100371243C (en) * | 2006-03-03 | 2008-02-27 | 中国科学院上海硅酸盐研究所 | Composite powder of nanomer tin dioxide particle in-situ coated carbon nanotube and its prepn process |
| CN100384782C (en) * | 2006-10-17 | 2008-04-30 | 山东大学 | Method for cladding Nano carbon tube by using hydroxyapatite |
| CN101491699B (en) * | 2009-03-03 | 2011-09-14 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced bone-cement biological composite material |
| CN101491696B (en) * | 2009-03-03 | 2011-09-14 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced hydroxylapatite composite material |
| CN102471049B (en) * | 2009-06-30 | 2015-08-26 | 韩华石油化学株式会社 | The blending of carbon nanotubes improves carbon complex and continuous production method and apparatus thereof |
| CN102471049A (en) * | 2009-06-30 | 2012-05-23 | 韩华石油化学株式会社 | Blending improvement carbon-composite having carbon-nanotube and its continuous manufacturing method and apparatus |
| US9567222B2 (en) | 2009-06-30 | 2017-02-14 | Hanwha Chemical Corporation | Blending improvement carbon-composite having carbon-nanotube and its continuous manufacturing method and apparatus |
| CN102502556A (en) * | 2011-12-14 | 2012-06-20 | 江南大学 | Method for preparing nano hydroxyapatite |
| CN104998301A (en) * | 2015-08-12 | 2015-10-28 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
| CN104998301B (en) * | 2015-08-12 | 2017-05-24 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
| CN106835847A (en) * | 2017-03-13 | 2017-06-13 | 南昌大学 | A kind of preparation method of bio-compatibility carbon nanometer tube/hydroxyapatite extrusion coating paper |
| CN107012720A (en) * | 2017-03-13 | 2017-08-04 | 南昌大学 | A kind of conductive non-woven fabrics preparation method of bio-compatible |
| CN108675281A (en) * | 2018-03-30 | 2018-10-19 | 西南交通大学 | It is a kind of to have electric conductivity and magnetic carbon nanotube based composites and preparation method thereof concurrently |
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