CN102126709A - Preparation method of boron nitride one-dimensional nanostructure macroscopic rope - Google Patents
Preparation method of boron nitride one-dimensional nanostructure macroscopic rope Download PDFInfo
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- CN102126709A CN102126709A CN2010100101555A CN201010010155A CN102126709A CN 102126709 A CN102126709 A CN 102126709A CN 2010100101555 A CN2010100101555 A CN 2010100101555A CN 201010010155 A CN201010010155 A CN 201010010155A CN 102126709 A CN102126709 A CN 102126709A
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Abstract
The invention relates to the field of boron nitride one-dimensional nanostructures, in particular to a preparation method of an oriented boron nitride one-dimensional nanostructure macroscopic rope. The method comprises the following steps of: volatilizing ferrocene serving as a floating catalyst precursor in a low-temperature region, carrying the volatilized precursor into a high-temperature region by using carrier gas so as to be decomposed into a metal catalyst, and promoting the reaction of diboron dioxide steam generated by the reaction of boron power in the high-temperature region with boron oxide with a nitrogen source by taking Fe2O3, FeS and ZnS as reaction promoting agents to generate a boron nitride one-dimensional nanostructure; stabilizing air stream by using a reaction casing in a reaction furnace to make the generated boron nitride one-dimensional nanostructure form a loose macroscopic rope structure through self-assembly; and fully soaking the loose macroscopic rope structure in an ethanol solution and assembling a dense boron nitride one-dimensional nanostructure macroscopic rope by using a boron nitride oriented nanostructure under the action of the surface tension of an ethanol-atmospheric air liquid surface. By adopting the method, damage to the structure by subsequent treatment assembly, molding and the like is avoided, and the excellent intrinsic properties of the boron nitride one-dimensional nanostructure are kept.
Description
Technical field:
The present invention relates to boron nitride one dimension Nano structure field, be specially a kind of preparation method of directed boron nitride nanostructure macroscopic view rope.
Background technology:
The boron nitride one dimension Nano structure is a kind of wide band gap semiconducter, has excellent performance and application prospects.Because its strong covalent bonds makes it have the mechanical property suitable with carbon nanotube, simultaneously because its high chemical stability and oxidation-resistance more make it use as equal acquisition of mechanics enhancing under severe condition such as high temperature, oxidizing atmosphere.Since nineteen ninety-five is found first, developed several different methods and prepare boron nitride nanostructure, for example arc process, laser splash method, chemical vapour deposition and solid reaction process etc.Wherein, chemical gaseous phase depositing process since have with low cost, controllability good and be easy to advantage such as amplification, be widely used.Utilize this method, realized the high purity of boron nitride nano-tube, relatively large preparation.
Needing in the practical application nanostructure is assembled into macroscopic material, how to realize connection, the assembling of boron nitride one dimension Nano structure, and forming the excellent properties that macroscopic material shows nanostructure later on, is emphasis and difficult point in the research at present.
Summary of the invention:
The object of the invention provides a kind of preparation method of boron nitride one dimension Nano structure macroscopic view rope, realizes connection, the assembling of boron nitride one dimension Nano structure, and is forming the excellent properties that macroscopic material shows nanostructure later on.
Technical scheme of the present invention is:
A kind of preparation method of boron nitride one dimension Nano structure macroscopic view rope, this method adopts horizontal chemical vapour deposition tubular react furnace, with ferrocene as floating catalytic agent presoma, floating catalytic agent presoma volatilizees and is carried to the high-temperature zone by carrier gas at cold zone and is decomposed into metal catalyst, promotes the boron powder and the boron oxide (B of high-temperature zone
2O
3) the titanium dioxide two boron (B that generate of reaction
2O
2) steam and nitrogenous source reaction generation boron nitride one dimension Nano structure.Simultaneously, play the effect of steady air flow, make the boron nitride one dimension Nano structure self-assembly that generates form loose macroscopical rope-like constructed by the reaction sleeve pipe in the Reaktionsofen.
Wherein:
The weight ratio of boron powder and boron oxide is between 1: 1～1: 7.
The temperature of reaction of cold zone is 100-300 ℃, and the temperature of reaction of high-temperature zone is 1200～1500 ℃.
It is (0.5～2) that the part by weight of floating catalytic agent presoma and reactant boron powder, boron oxide summation closes: 1.
The throughput ratio of carrier gas and nitrogenous source is 0.25～6: between 1, the gas flow of nitrogenous source is 10～200 ml/min.
B
2O
2Steam and nitrogenous source constant temperature 60～180 minutes under temperature of reaction, reaction promotor adopts Fe
2O
3, FeS and ZnS, Fe
2O
3, FeS and ZnS part by weight be 2: 1: 2, it is (0.25～0.5) that the part by weight of reaction promotor and reactant boron powder, boron oxide summation closes: 1.
The boron nitride one dimension Nano structure can be boron nitride nano-tube or boron nitride nanometer fiber.Wherein,
(the 0.1-0.5 weight part does not comprise 0.5) can obtain boron nitride nano-tube under the less situation of floating catalytic agent presoma usage quantity, the internal diameter 20～40nm of boron nitride nano-tube, wall thickness 5～10nm;
Under the big situation of floating catalytic agent presoma usage quantity (0.5-1 weight part), can obtain the boron nitride nanometer fiber, the about 100～200nm of the diameter of boron nitride nanometer fiber.
In addition, the boron nitride one dimension Nano structure for preparing was soaked in ethanolic soln one hour, fully soak into, mention gently with tweezers then.Because by ethanol-atmosphere liquid level surface tension effects, it is fine and close that loose boron nitride structure becomes, and keeps its original high oriented alignment simultaneously, thereby handle and be assembled into fine and close boron nitride one dimension Nano structure macroscopic view rope by liquid-gas interface.The length of macroscopic view rope can reach 0.5～5 cm, and the diameter of macroscopic view rope can reach 1 μ m to 1mm.
The invention has the beneficial effects as follows:
1, the present invention proposes the self-assembly preparation method thereof of boron nitride one dimension Nano structure macroscopic view rope, the macroscopical rope form boron nitride structure original position in preparation process that is cm-level length forms by self-assembly, avoid subsequent disposal assembling, moulding etc. that its structure is damaged, thereby kept the intrinsic performance of boron nitride one dimension Nano structure excellence.
2, on self-assembly synthetic basis, prepared the boron nitride fibre of compact structure by the liquid-gas interface assembling.
3, the present invention lays the foundation for the application of boron nitride nanostructure in the structure reinforced composite.
Description of drawings:
Fig. 1. the preparation facilities structural representation of boron nitride one dimension Nano structure macroscopic view rope.
Among the figure, 1 floating catalytic agent presoma; 2 reactants; 3 graphite flakes; 4 thermopairs; 5 reaction vessels; 6 inlet pipe; 7 vapor pipes; 8 reaction sleeve pipes.
Fig. 2. the characterization result of prepared boron nitride one dimension Nano structure macroscopic view rope among the embodiment 1.Wherein, (a-b) electron scanning micrograph; (c-d) transmission electron microscope photo.
Fig. 3. the electron scanning micrograph that the boron nitride nanostructure macroscopic view is restricted after operation of process liquid-gas interface and the assembling among the embodiment 2.Wherein, (a) figure is a macrograph; (b) figure is the high power photo.
Fig. 4. boron nitride nanostructure electron scanning micrograph among the embodiment 3.Wherein, (a) figure is a boron nitride high-purity nano tubular construction; (b) compact nanometer pipe.
Embodiment:
As shown in Figure 1, the present invention is used to prepare the horizontal chemical vapour deposition tubular react furnace of device employing of boron nitride one dimension Nano structure macroscopic view rope, and concrete structure is as follows:
The reaction vessel 5 of this device is a tubular structure, its internal diameter is 40～60mm, reaction vessel 5 outsides are provided with the electrically heated part, reaction sleeve pipe 8 is set in the reaction vessel 5, reaction sleeve pipe 8 is the alundum tube of internal diameter 30-40mm, and reaction vessel 5 two ends connect inlet pipe 6 and vapor pipe 7 respectively, and inlet pipe 6 extends in the reaction sleeve pipe 8, thermopair 4 extends the inner chamber of reaction vessel 5, and thermometric and temperature control are realized by thermopair and computer program.Be divided into high-temperature zone and cold zone two portions in the reaction sleeve pipe 8 in the reaction vessel 5, the high-temperature zone is positioned at the middle part of reaction vessel 5, cold zone is positioned at an end of reaction vessel 5, high-temperature zone placing response thing 2 in reaction sleeve pipe 8 and reaction promotor are on graphite flake 3, cold zone in reaction sleeve pipe 8 is placed floating catalytic agent presoma 1, imports carrier gas (Ar) and nitrogen source gas (NH by inlet pipe 6 after heating up
3).
The present invention adopts floating catalytic thinner CVD (Chemical Vapor Deposition) method, with ferrocene as floating catalytic agent presoma, floating catalytic agent presoma is in cold zone distillation volatilization, and be carried to the high-temperature zone by carrier gas and be decomposed into nano metal (Fe) particle, as the catalyzer of boron nitride (BN) nanostructure growth, promote the B that the reaction of boron powder and boron oxide generates
2O
2Steam and ammonia gas react generate the boron nitride one dimension Nano structure.Simultaneously, by the reaction sleeve pipe in the Reaktionsofen air-flow is controlled, the boron nitride one dimension Nano structure is oriented alignment under the air-flow effect, the boron nitride one dimension Nano structure self-assembly that generates forms macroscopical rope-like constructed, and handle and be assembled into dense structure by liquid-gas interface, after reaction is finished at reaction sleeve pipe afterbody collection sample.
Embodiment 1
Floating catalytic agent presoma is ferrocene 0.8g, it is 0.5: 1 that the part by weight of its usage quantity and reactant (boron powder, boron oxide) summation closes, vaporization temperature is 150 ℃, ammonia flow is 50 ml/min, argon flow amount is 300 ml/min, boron powder and boron oxide weight ratio 1: 7, reaction promotor adopts Fe
2O
3, FeS and ZnS, Fe
2O
3, FeS and ZnS part by weight be 2: 1: 2, it is 0.3: 1 that the part by weight of reaction promotor and reactant boron powder, boron oxide summation closes, 1350 ℃ of temperature of reaction, 30 ℃/min of temperature rise rate, 2 hours reaction times.Obtain about about 200 nanometers of diameter, length is 100～200 microns boron nitride nanometer fiber (single fiber), play the effect of steady air flow by the reaction sleeve pipe in the Reaktionsofen, make the boron nitride nanometer fiber self-assembly that generates form loose macroscopical rope-like constructed, characterization result is seen Fig. 2.From electron scanning micrograph as can be seen, boron nitride nanostructure aligns, but comparatively loose, and a lot of holes and fork are arranged.Can be clearly seen that the arrangement that (0002) is perpendicular to axial direction from high resolution picture, its purity is about 95wt%.
Embodiment 2
Embodiment 1 prepared boron nitride oriented structure was soaked in ethanolic soln 1 hour, fully soak into, mention gently with tweezers then.Because it is fine and close that capillary effect, loose boron nitride structure become, and keeps its original high oriented alignment simultaneously.According to the difference of the boron nitride nanostructure amount of using, the diameter that can control the close micrometer fibers macroscopic view of boron nitride rope at 1 μ m between the 1mm, length at 0.5cm between the 5cm.
As shown in Figure 3, from electron scanning micrograph as can be seen, the about 250 μ m of diameter of the close micrometer fibers macroscopic view of present embodiment boron nitride rope, fine and close, basic not fork keeps original oriented alignment mode simultaneously.
Embodiment 3
Floating catalytic agent presoma is ferrocene 0.3g, it is 1: 1 that the part by weight of its usage quantity and reactant (boron powder, boron oxide) summation closes, vaporization temperature is 200 ℃, ammonia flow is 100 ml/min, argon flow amount is 100 ml/min, boron powder and boron oxide weight ratio 1: 1, reaction promotor adopts Fe
2O
3, FeS and ZnS, Fe
2O
3, FeS and ZnS part by weight be 2: 1: 2, it is 0.5: 1 that the part by weight of reaction promotor and reactant boron powder, boron oxide summation closes, 1500 ℃ of temperature of reaction, 20 ℃/min of temperature rise rate, 3 hours reaction times.Obtain the boron nitride nano-tube (single nanotube) of 50～80 microns of internal diameter 20～40nm, wall thickness 5～10nm, length, play the effect of steady air flow by the reaction sleeve pipe in the Reaktionsofen, make the boron nitride one dimension Nano structure self-assembly that generates form loose macroscopical rope-like constructed, characterization result is seen Fig. 4.From electron scanning micrograph as can be seen, boron nitride nanostructure aligns, but comparatively loose, and a lot of holes and fork are arranged.Can be clearly seen that the arrangement that (0002) is perpendicular to axial direction from high resolution picture, its purity is about 95wt%.
The boron nitride nano-tube of preparation soaked in ethanolic soln 1 hour, fully soaked into, and mentioned gently with tweezers then.The diameter that forms the fine and close macroscopic view rope of boron nitride at 1 μ m between the 1mm, length at 0.5cm between the 5cm.
As shown in Figure 4, from electron scanning micrograph as can be seen, present embodiment boron nitride high-purity nano tubular construction (a) becomes the about 25 μ m of diameter of fine and close macroscopic view rope (b) by the liquid-gas interface operational transition.
Claims (10)
1. the preparation method of boron nitride one dimension Nano structure macroscopic view rope, it is characterized in that: this method adopts horizontal chemical vapour deposition tubular react furnace, reaction sleeve pipe in the Reaktionsofen is divided into high-temperature zone and cold zone, floating catalytic agent presoma is positioned over cold zone, and boron powder and boron oxide are positioned over the high-temperature zone; With ferrocene as floating catalytic agent presoma, floating catalytic agent presoma volatilizees and is carried to the high-temperature zone by carrier gas at cold zone and is decomposed into metal catalyst, promotes the boron powder of high-temperature zone and titanium dioxide two boron vapours and nitrogenous source reaction generation boron nitride one dimension Nano structure that the boron oxide reaction generates; Simultaneously, play the effect of steady air flow, make the boron nitride one dimension Nano structure self-assembly that generates form loose macroscopical rope-like constructed by the reaction sleeve pipe in the Reaktionsofen.
2. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: the weight ratio of boron powder and boron oxide is between 1: 1～1: 7.
3. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: the temperature of reaction of cold zone is 100-300 ℃, and the temperature of reaction of high-temperature zone is 1200～1500 ℃.
4. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: it is (0.5～2) that the part by weight of floating catalytic agent presoma and reactant boron powder, boron oxide summation closes: 1.
5. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: the throughput ratio of carrier gas and nitrogenous source is 0.25～6: between 1, the gas flow of nitrogenous source is 10～200 ml/min.
6. according to the preparation method of the described boron nitride one dimension Nano structure of claim 1 macroscopic view rope, it is characterized in that: titanium dioxide two boron vapours and nitrogenous source constant temperature 60～180 minutes under temperature of reaction.
7. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: be provided with reaction promotor in the high-temperature zone, reaction promotor adopts Fe
2O
3, FeS and ZnS, Fe
2O
3, FeS and ZnS part by weight be 2: 1: 2, it is (0.25～0.5) that the part by weight of reaction promotor and reactant boron powder, boron oxide summation closes: 1.
8. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: the boron nitride one dimension Nano structure is boron nitride nano-tube or boron nitride nanometer fiber.
9. according to the macroscopical preparation method who restricts of the described boron nitride one dimension Nano structure of claim 1, it is characterized in that: loose boron nitride one dimension Nano structure macroscopic view rope was soaked one hour in ethanolic soln, fully soak into, by ethanol-atmosphere liquid level surface tension effects, the boron nitride oriented nano structure is assembled into fine and close boron nitride one dimension Nano structure macroscopic view rope.
10. according to the preparation method of the described boron nitride one dimension Nano structure macroscopic view of claim 1 rope, it is characterized in that: the diameter of the boron nitride one dimension Nano structure macroscopic view rope of described densification is controlled at 1 μ m between the 1mm, and length is controlled at 0.5cm to 5cm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528671A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method of porous boron nitride nanofibers |
| CN104743530A (en) * | 2015-03-31 | 2015-07-01 | 盐城工学院 | Method for preparing boron nitride nano-fibres by virtue of arc discharge |
| WO2017155468A1 (en) * | 2016-03-09 | 2017-09-14 | Nanyang Technological University | Chemical vapor deposition process to build 3d foam-like structures |
| CN108584891A (en) * | 2018-07-20 | 2018-09-28 | 芜湖清柏白露智能信息科技有限公司 | A kind of preparation method of boron nitride nanometer band |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281481C (en) * | 2004-07-08 | 2006-10-25 | 北京理工大学 | Process for preparing boron nitride nano tube |
| CN100526217C (en) * | 2006-04-29 | 2009-08-12 | 中国科学院金属研究所 | Preparation method of quasi one-dimensional boron nitride nanostructure |
| CN101513995B (en) * | 2009-04-01 | 2010-12-29 | 武汉工程大学 | Method for preparing boron nitride nano-tube |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528671A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method of porous boron nitride nanofibers |
| CN104743530A (en) * | 2015-03-31 | 2015-07-01 | 盐城工学院 | Method for preparing boron nitride nano-fibres by virtue of arc discharge |
| WO2017155468A1 (en) * | 2016-03-09 | 2017-09-14 | Nanyang Technological University | Chemical vapor deposition process to build 3d foam-like structures |
| CN108699684A (en) * | 2016-03-09 | 2018-10-23 | 南洋理工大学 | Chemical vapour deposition technique builds three-dimensional foam shape structure |
| CN108699684B (en) * | 2016-03-09 | 2021-08-24 | 南洋理工大学 | Chemical vapor deposition process for building three-dimensional foam-like structures |
| US11104989B2 (en) | 2016-03-09 | 2021-08-31 | Nanyang Technological University | Chemical vapor deposition process to build 3D foam-like structures |
| CN108584891A (en) * | 2018-07-20 | 2018-09-28 | 芜湖清柏白露智能信息科技有限公司 | A kind of preparation method of boron nitride nanometer band |
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