CN101156961B - Method for preparing carbon nanometer tube/hydroxyapatite complex powder through in-situ vapour deposition reaction - Google Patents
Method for preparing carbon nanometer tube/hydroxyapatite complex powder through in-situ vapour deposition reaction Download PDFInfo
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- CN101156961B CN101156961B CN2007101501356A CN200710150135A CN101156961B CN 101156961 B CN101156961 B CN 101156961B CN 2007101501356 A CN2007101501356 A CN 2007101501356A CN 200710150135 A CN200710150135 A CN 200710150135A CN 101156961 B CN101156961 B CN 101156961B
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Abstract
The invention discloses a preparation method of carbon nano-tube/hydroxyapatite composite powder, and belongs to the preparation technology of hydroxyapatite composite matrix composite material. The processes of the method are as follows: ferric nitrate and hydroxyapatite powder are taken as raw materials, according to a certain mass ratio, a deposition-sedimentation method is adopted to prepare Fe/HA catalytic agent precursor Fe2O3/HA, the precursor Fe2O3/HA is utilized to prepare CNTs/HA composite powder with nitrogen gas and methane as reaction gases and through a chemical gas phase deposition method under a certain temperature. The invention has the advantages that the preparation process is simple, and the catalytic agent adopted is no poisoning to the human body; the quality of the carbon nano-tube in the power body is good, the purity rate is high, and the size is even; the carbon nano-tube is dispersed evenly in the hydroxyapatite power body, and the combination of the carbon nano-tube with the matrix is good; the power body is the ideal raw material to prepare the composite material of the CNTs/HA.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanometer tube/hydroxyapatite complex powder.The technology of preparing that belongs to the hydroxyapatite based composites.
Background technology
Hydroxyapatite (HA) is one of bioactive hard tissue implanting material of tool of generally acknowledging in the world at present, nontoxic, do not have carcinogenesis and have excellent biological compatibility, be widely used in fields such as shaping and esthetic surgery, tooth section, chromatography purification, nutrient calcium supplementing, but its relatively poor comprehensive mechanical property, low bending strength and fracture toughness have all limited its practical application greatly.In the world, CNT (CNTs) has been acknowledged as a kind of structural material of excellent performance, its sealing hollow tubular structure has good stable, and have minimum yardstick and excellent mechanical property, its Young's modulus of theoretical calculation is up to 5TPa, and intensity is about 100 times of steel and density has only 1/6 of steel, is present specific strength and the highest material of specific stiffness, therefore, CNTs has important use value as 1-dimention nano whisker reinforcing material in composite.At present, CNTs is applied to HA is toughness reinforcing, the mechanical blending method is mainly adopted in plasticising, repress is made composite after promptly HA powder and CNTs mechanical mixture being obtained the CNTs/HA powder, though this method is simple, but can not solve at all CNTs in the HA matrix dispersion and and HA between interface pollution and infiltration problem, this is the primary difficult problem that development CNTs/HA composite faces.
Summary of the invention
The object of the invention is to provide a kind of method of preparing carbon nanometer tube/hydroxyapatite complex powder through vapour deposition reaction in-situ, CNTs/HA composite powder with this method preparation can significantly improve the distribution situation of CNTs in HA, can obtain to have the CNTs/HA composite powder that CNTs is uniformly dispersed, CNTs-HA does not have interface pollution and wellability is good.
The present invention is realized by the following technical programs, and a kind of method of preparing carbon nanometer tube/hydroxyapatite complex powder through vapour deposition reaction in-situ is characterized in that comprising following process,
1) preparation catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2
Is (0.073-0.48) with nine water ferric nitrates and HA powder in mass ratio: 1 ratio joins in the deionized water, being mixed with concentration is the nine liquid glauber salt acid ferrous solution that 0.05mol/L contains HA, make precipitant with sodium hydroxide or ammonia, the following dropping of stirring precipitant to solution is pH and equals 7, makes Fe/Ca
10(PO
4)
6(OH)
2Mass ratio is (0.001-0.1): 1 Fe (OH)
3/ Ca
10(PO
4)
6(OH)
2Binary colloidal; This binary colloidal is dewatered under 150 ℃-300 ℃, nitrogen atmosphere, and, obtain Fe/Ca at 350 ℃ of-500 ℃ of temperature lower calcinations
10(PO
4)
6(OH)
2Catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2
2) preparation CNTs/HA composite powder
The catalyst precursor Fe that step 1) is made
2O
3/ Ca
10(PO
4)
6(OH)
2Powder is layered in the quartz boat, and quartz boat is placed flat-temperature zone, reaction tube middle part; Feed nitrogen and get rid of inner air tube, be warming up to 450-650 ℃ then; Feed hydrogen with 25-400ml/min to reactor, and maintenance 1.5-4h, close hydrogen afterwards, with volume ratio is (1-12): 1 the nitrogen and the gaseous mixture of methane, feed reactor with 300-900ml/min, under 400-650 ℃, carry out catalytic cracking reaction 1-4h, stop the mist air inlet afterwards, reactor is chilled to room temperature under nitrogen atmosphere, obtain the CNTs/HA composite powder.
The present invention has the following advantages:
Catalyst system therefor Fe is that human body must trace element, to human body nonhazardous effect, thereby save operation such as CNT purification, so technical process is simple; Make that CNTs quality in the powder body is good, purity is high, caliber be 10-30nm and size evenly, boss ratio is 0.4-0.7; CNTs is uniformly dispersed in the composite granule that makes, and do not have interface pollution between HA, wellability is good, becomes the desirable raw material of preparation CNTs/HA composite;
Description of drawings
Fig. 1 is the SEM figure of example 1 obtained CNTs/HA composite powder of the present invention.
Fig. 2 is the TEM figure of the CNTs in the example 1 prepared composite granule of the present invention.
Fig. 3 is the HRTEM figure of the CNTs in the example 1 prepared composite granule of the present invention.
The specific embodiment
Further specify the present invention below in conjunction with embodiment, these embodiment only are used to illustrate the present invention, do not limit the present invention.
The raw material that uses: nine water ferric nitrates, commercially available, purity＞96%; The HA powder, commercially available, 400 orders.
Embodiment 1
0.056g nine water ferric nitrates and 1.287gHA powder are joined in the deionized water, being mixed with concentration is the nine liquid glauber salt acid ferrous solution that 0.05mol/L contains HA, the sodium hydroxide solution that drips 0.05mol/L in solution is also precipitated pH value of solution=7.0, makes Fe/Ca
10(PO
4)
6(OH)
2Mass ratio is 0.01: 1 Fe (OH)
3/ Ca
10(PO
4)
6(OH)
2Binary colloidal; This binary colloidal is dewatered under 250 ℃, nitrogen atmosphere, and, obtain Fe/Ca at 450 ℃ of temperature lower calcinations
10(PO
4)
6(OH)
2Catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2With prepared Fe/Ca
10(PO
4)
6(OH)
2Catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2Powder is layered in the quartz boat, and quartz boat is placed flat-temperature zone, reaction tube middle part; Feed nitrogen and get rid of inner air tube, be warming up to 550 ℃ then; Feed hydrogen with 200ml/min to reactor, and maintenance 2h, close hydrogen afterwards, gaseous mixture with 420ml/min nitrogen and 60ml/min methane feeds reactor, under 550 ℃, carry out catalytic cracking reaction 1h, stop the gaseous mixture air inlet afterwards, make reactor under nitrogen atmosphere, be chilled to room temperature, make the CNTs/HA composite powder, the CNTs productive rate is 0.03%, record its average diameter with the digital micrograph image software is that 11nm, average length are 2 μ m.
Embodiment 2
The experiment condition of present embodiment and process are with embodiment 1, and difference is that the catalytic cracking reaction time is 2h, makes the CNTs/HA composite powder, and the CNTs productive rate is 0.05%, average diameter is that 13nm, average length are 2.7 μ m.
Embodiment 3
The experiment condition of present embodiment and process are with embodiment 1, and difference is that the catalytic cracking reaction temperature is 650 ℃, makes the CNTs/HA composite powder, and the CNTs productive rate is 0.06%, average diameter is that 14nm, average length are 2.4 μ m.
Embodiment 4
0.281g nine water ferric nitrates and 1.235gHA powder are joined in the deionized water, being mixed with concentration is the nine liquid glauber salt acid ferrous solution that 0.05mol/L contains HA, the sodium hydroxide solution that drips 0.05mol/L in solution makes solution be neutral and is precipitated, and makes the Fe/HA mass ratio and be 0.05: 1 Fe (OH)
3/ Ca
10(PO
4)
6(OH)
2Binary colloidal; The step of CNTs/HA composite powder preparation afterwards is identical with embodiment 1 with condition, and the productive rate that makes CNTs is 1.1%, average diameter is that 16nm, average length are 4 μ m.
Embodiment 5
The experiment condition of present embodiment and process are with embodiment 4, and difference is that the catalytic cracking reaction time is 2h, makes the CNTs/HA composite powder, and the CNTs productive rate is 1.22%, average diameter is that 18nm, average length are 5.7 μ m.
Embodiment 6
The experiment condition of present embodiment and process are with embodiment 4, and difference is that the catalytic cracking reaction temperature is 650 ℃, makes the CNTs/HA composite powder, and the CNTs productive rate is 1.29%, average diameter is that 19nm, average length are 6.2 μ m.
Embodiment 7
Is that 0.48: 1 ratio joins in the deionized water with 0.562g nine water ferric nitrates and 1.170gHA powder in mass ratio, being mixed with concentration is the nine liquid glauber salt acid ferrous solution that 0.05mol/L contains HA, the sodium hydroxide solution that drips 0.05mol/L in solution makes solution be neutral and is precipitated, and makes the Fe/HA mass ratio and be 0.1: 1 Fe (OH)
3/ Ca
10(PO
4)
6(OH)
2Binary colloidal; The step of CNTs/HA composite powder preparation afterwards is identical with embodiment 1 with condition, makes the CNTs productive rate and be 2.34%, average diameter is that 21nm, average length are 7 μ m.
Embodiment 8
The experiment condition of present embodiment and process are with embodiment 7, and difference is that the catalytic cracking reaction time is 2h, makes the CNTs/HA composite powder, and the CNTs productive rate is 2.37%, average diameter is that 24nm, average length are 7.6 μ m.
Embodiment 9
The experiment condition of present embodiment and process are with embodiment 1, difference is to feed reactor with the gaseous mixture of 400ml/min nitrogen and 80ml/min methane, make the CNTs/HA composite powder, the CNTs productive rate is 0.06%, average diameter is that 14nm, average length are 3.1 μ m.
Embodiment 10
The experiment condition of present embodiment and process are with embodiment 1, difference is to feed reactor with the gaseous mixture of 440ml/min nitrogen and 40ml/min methane, make the CNTs/HA composite powder, the CNTs productive rate is 0.01%, average diameter is that 9nm, average length are 1.5 μ m.
Claims (1)
1. the method for a preparing carbon nanometer tube/hydroxyapatite complex powder through vapour deposition reaction in-situ is characterized in that comprising following process,
1) preparation catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2
Is (0.073-0.48) with nine water ferric nitrates and hydroxyapatite powder in mass ratio: 1 ratio joins in the deionized water, being mixed with concentration is the nine liquid glauber salt acid ferrous solution that 0.05mol/L contains hydroxyapatite, make precipitant with sodium hydroxide or ammonia, the following dropping of stirring precipitant to solution is pH and equals 7, makes Fe/Ca
10(PO
4)
6(OH)
2Mass ratio is (0.001-0.1): 1 Fe (OH)
3/ Ca
10(PO
4)
6(OH)
2Binary colloidal; This binary colloidal is dewatered under 150 ℃-300 ℃, nitrogen atmosphere, and, obtain Fe/Ca at 350 ℃ of-500 ℃ of temperature lower calcinations
10(PO
4)
6(OH)
2Catalyst precursor Fe
2O
3/ Ca
10(PO
4)
6(OH)
2
2) preparation carbon nanometer tube/hydroxyapatite complex powder
The catalyst precursor Fe that step 1) is made
2O
3/ Ca
10(PO
4)
6(OH)
2Powder is layered in the quartz boat, and quartz boat is placed flat-temperature zone, reaction tube middle part; Feed nitrogen and get rid of inner air tube, be warming up to 450-650 ℃ then; Feed hydrogen with 25-400ml/min to reactor, and kept 1.5-4 hour, close hydrogen afterwards, with volume ratio is (1-12): 1 the nitrogen and the gaseous mixture of methane, feed reactor with 300-900ml/min, under 400-650 ℃, carried out catalytic cracking reaction 1-4 hour, stop the mist air inlet afterwards, reactor is chilled to room temperature under nitrogen atmosphere, obtain the carbon nanometer tube/hydroxyapatite complex powder composite powder.
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| CN2007101501356A CN101156961B (en) | 2007-11-12 | 2007-11-12 | Method for preparing carbon nanometer tube/hydroxyapatite complex powder through in-situ vapour deposition reaction |
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|---|---|---|---|
| CN2007101501356A CN101156961B (en) | 2007-11-12 | 2007-11-12 | Method for preparing carbon nanometer tube/hydroxyapatite complex powder through in-situ vapour deposition reaction |
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| CN101156961B true CN101156961B (en) | 2010-06-09 |
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| CN101318034B (en) * | 2008-05-08 | 2011-07-27 | 西南交通大学 | Method for in situ growth for preparing nano-composite material of carbon nano-tube and hydroxyapatite |
| CN101905036A (en) * | 2009-06-04 | 2010-12-08 | 佳木斯大学 | Novel hydroxyapatite/SiOC biological ceramic composite material and preparation method thereof |
| CN102000363B (en) * | 2010-11-10 | 2013-05-15 | 东华大学 | Preparation method of CA/CS/CNTs (cellulose acetate/chitosan/ carbon nano tubes) composite nano fiber with good biocompatibility |
| CN102552978A (en) * | 2012-02-20 | 2012-07-11 | 西北工业大学 | Method for preparing hydroxyapatite bioactive coating |
| CN102976743B (en) * | 2012-12-19 | 2014-03-19 | 河北工业大学 | Preparation method of carbon nanotube reinforced hydroxyapatite composite material |
| CN104692348B (en) * | 2015-03-22 | 2016-08-24 | 河北工业大学 | Prepare double in-situ synthetic methods of carbon nano-tube reinforced hydroxylapatite composite material |
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2007
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Non-Patent Citations (2)
| Title |
|---|
| 于志云.纳米碳管/羟基磷灰石生物复合材料的凝胶注模成型技术研究.山东大学硕士论文,2006,全文. * |
| 魏强.多壁碳纳米管/纳米羟基磷灰石骨修复复合材料的研究初步.北京化工大学硕士论文,2004,全文. * |
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