CN103803513B - Preparation method of boron nitride nanotube - Google Patents
Preparation method of boron nitride nanotube Download PDFInfo
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- CN103803513B CN103803513B CN201410091384.2A CN201410091384A CN103803513B CN 103803513 B CN103803513 B CN 103803513B CN 201410091384 A CN201410091384 A CN 201410091384A CN 103803513 B CN103803513 B CN 103803513B
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Abstract
The invention relates to a preparation method of a boron nitride nanotube. The preparation method comprises the following steps: bringing mono-element precursor borazine into a deposition hearth by utilizing carrier gas and dilute gas and by adopting carbon nanotube as a template in a chemical vapor deposition furnace, decomposing the borazine to boron nitride in the deposition furnace under the condition of a given vacuum degree and deposition temperature, and depositing the boron nitride onto the surface of the carbon nanotube; removing the carbon in an oxidation manner so as to obtain the boron nitride nanotube. Different application requirements can be met only by controlling the vacuum degree, deposition temperature and the flow rate of the carrier gas and the dilute gas in the hearth of the deposition furnace, the process is simple, convenience in operation can be realized, and no other impurity element is introduced except the carbon; the carbon can be removed in the oxidation manner in the air or oxygen, so that the boron nitride nanotube with the purity of more than or equal to 98 percent can be obtained; meanwhile, the size and diameter of the boron nitride nanotube can be controlled by adopting different template carbon nanotubes of different specifications.
Description
Technical field
The present invention relates to the preparation method of nano material, specifically, relate to a kind of method that chemical vapor deposition method prepares boron nitride nano-tube.
Background technology
Boron nitride nano-tube is the novel nano material of a class, it not only has good chemical stability, excellent mechanical property, good antioxidant property, also there is broad-band gap, good electrical properties etc., make it all have good application prospect in multiple technical field such as matrix material, electron device.
CN 1208245C discloses a kind of method preparing boron nitride nano-tube: by chemical pure H
3bO
3, CO (NH
2)
2with Fe (NO
3)
39H
2o or Co (NO
3)
26H
2o, or Ni (NO
3)
26H
2o is dissolved in deionized water together; Evaporate the water in solution, obtain the powder mixed; Mixed powder is placed in the horizontal chamber oven communicated with air to heat, when temperature rises to 1000-1300 DEG C, constant temperature 60-90 minute; Be down to room temperature, obtain pale powder; Soak described pale powder with dust technology, removing catalyzer, obtains the pure BN-NTs of white.
The method preparing boron nitride nano-tube disclosed in CN 1281481C is, select boron oxide, boric acid etc. containing boron and avirulent boron compound is raw material, first ball milling certain hour, then more than the ammonia of flowing or heated under nitrogen to 800 DEG C, insulation more than 0.5h.Take out after cooling, with dilute hydrochloric acid, distilled water and ethanol, rear drying is cleaned to sample, obtain white powder and be boron nitride nano-tube.
CN100369806C discloses a kind of method of synthesizing single shape boron nitride nano tube: using ammonia and boron powder as nitrogenous source and boron source, with Si and Nano-meter SiO_2
2powder is as catalyzer, and under the temperature condition of 1000 DEG C-1300 DEG C, reaction 60-120 minute, by controlling the atmosphere of reaction process, the boron nitride nano-tube of synthesizing single shape in same reaction system.
CN 1970437A discloses a kind of method of preparing boron nitride nanotube by arc discharge: using nitrogen and boron powder as nitrogenous source and boron source, with transition metal oxide Fe
2o
3, NiO or Co
3o
4nanometer powder as catalyzer, in electric arc furnace, boron nitride nano-tube is prepared in exoelectrical reaction.
CN 101348242A discloses a kind of method of preparing boron nitride nanotube by magnesium reduction: under argon shield, sieves after boron oxide, magnesium and ferrous salt ground and mixed; Heat the mixture after sieving under argon shield, when 900-1200 DEG C, close argon gas and also pass into ammonia, when temperature reaches 1200-1600 DEG C, constant temperature 1-5 hour; After temperature is down to room temperature, with nitric acid dousing products therefrom removing impurity, obtain boron nitride nano-tube.
Disclosed in CN 101513995B, the preparation method of boron nitride nano-tube is: reacted in nitrogen, ammonia or nitrogen-hydrogen mixed gas by boron source catalyst precursor, crude product is through separating-purifying, boron source catalyst precursor is made up of the mixture of boron-containing compound, magnesium powder, alkaline earth metal compound, transition-metal catalyst, the BN nanotube even thickness of preparation.
CN 101580236B discloses a kind of method of preparing boron nitride nanotubes by annealing of inorganic boracic precursor: anneal inorganic boracic catalyst precursor at 800-1200 DEG C 5-50 hour, obtains boron nitride nano-tube.
CN 101633498A discloses the preparation method of the controlled boron nitride nano-tube of a kind of size: by boron and catalyzer are placed in Plastic Bottle by weight 1: 0.01-0.05, using non-aqueous solvent as medium, ball milling 8-24 hour, after drying, sieves; Mixture after sieving is heated under argon shield condition, when temperature reaches 1000-1300 DEG C, stops passing into argon gas and passing into nitrogen or ammonia-nitrogen mixed gas, constant temperature 0.5-5 hour; Be down to room temperature after constant temperature terminates, products therefrom added nitric acid and carry out supersound process, the catalyzer that removing is residual, obtain boron nitride nano-tube.
Disclosed in CN 101717077A, the preparation method of boron nitride nano-tube is: the mixed powder of ammonia borine and catalyzer or ammonia borine are joined with in graphite paper or the filter paper crucible that is liner, again crucible is placed in air pressure stove, high pure nitrogen is filled with in air pressure stove, then heat up with the heat-up rate of 5-30 DEG C/min, be incubated again, then be cooled to room temperature, obtain boron nitride nano-tube.
CN 101786611A discloses a kind of Fe
3bO
6the method of boron nitride nano-tube is prepared in ammonification: raw material iron containing compounds and boron-containing compound are taked dry mixing process or the mixing of liquid phase recombining process, obtain mixing raw material, be pressed, then prepare Fe in insulation reaction
3bO
6, directly by Fe
3bO
6ammonification, products therefrom soaks through concentrated hydrochloric acid again, then centrifugation, and washing and drying, can obtain boron nitride nano-tube.
Disclosed in CN 101786884A, the preparation method of boron nitride nano-tube is, inorganic porous ceramic material is carried out aminating reaction 5-24 hour with ammonia at 800-1200 DEG C and obtains boron nitride nanotube crude product, elemental mole ratios example in described inorganic porous ceramic material is Mg: Fe: B: O=1: (0.10-1.65): (0.33-1.95): (0.5-5), then can obtain boron nitride nano-tube through separating-purifying.
Disclosed in CN 102674271A, the preparation method of boron nitride nano-tube is: in argon gas atmosphere, fluoroboric acid ammonia, sodium amide and reduced iron powder mixture are placed in special stainless steel cauldron and seal, put into the heating of resistance crucible furnace, product is through alcohol wash, pickling and be washed to neutrality, is separated drying and can obtains boron nitride nano-tube.
CN 102849694A discloses a kind of preparation method of batch preparation of boron nitride nanotube: by boron source, transistion metal compound and alkaline earth metal compound fully mix, mixture is heated to 1000 ~ 1100 DEG C under nitrogen or argon, stop passing into shielding gas, the mixed gas starting to pass into ammonia or nitrogen and hydrogen carries out reacting and continues to be heated to 1200 ~ 1400 DEG C, be incubated 0.5 ~ 4 hour, insulation terminates passing into of rear stopping gas, close into, air outlet also cools the temperature to room temperature, obtain white crude, after crude product is heated to 600 DEG C in atmosphere, pickling is dry, the caliber of prepared boron nitride nano-tube is 50 ~ 300nm, length can reach more than 100 microns.
CN 102874776A discloses the batch preparation that a kind of caliber is less than the boron nitride nano-tube of 100 nanometers: by unformed boron powder, transition metal oxide and CaO to immerse in the hydrochloric acid of 36 ~ 38wt% and stir, after transition metal oxide and CaO dissolve, add basic solution until there is precipitation, again after filtration, washing, drying is precipitated the mixture with unformed boron powder, stop after mixture is heated to 1000 ~ 1100 DEG C under nitrogen or argon passing into shielding gas, then the mixed gas passing into ammonia or nitrogen and hydrogen carries out reacting and continues to be heated to 1200 ~ 1400 DEG C, be incubated 0.5 ~ 4 hour, then room temperature is cooled the temperature to, obtain white crude, pickling after crude product is heated to 600 DEG C in atmosphere, dry, namely obtaining caliber is 3 ~ 100 nanometers, length is the boron nitride nano-tube of some tens of pm.
Above-mentioned disclosed boron nitride nanometer tube preparation method, needs to introduce metal oxide, metallic salt or other catalyzer, or needs multiple component such as introducing boron source and nitrogenous source etc. to carry out chemical reaction, its reaction is all more complicated, and be difficult to avoid being mixed into into impurity, obtained product, purity is less than 90%.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the above-mentioned deficiency of prior art, provides a kind of product purity high, the preparation method of boron nitride nano-tube easy and simple to handle.
The technical scheme that the present invention solves the employing of its technical problem is: in chemical vapor deposition stove, take carbon nanotube as template, with carrier gas and carrier gas, single constituent element precursor boron azine is brought in deposition burner hearth, make boron azine in cvd furnace, decomposite boron nitride and be deposited on carbon nano tube surface; Through oxidation removal carbon, namely obtain boron nitride nano-tube.
Concrete preparation method, comprises the following steps:
1) carbon nanotube is placed in organic solvent for ultrasonic cleaning, removes surface contaminant, after drying, put into chemical vapor deposition stove thorax;
2) controlling the vacuum tightness of cvd furnace is 0.01 ~ 2000Pa(preferably 1 ~ 1200Pa, more preferably 20 ~ 1100 Pa, further preferred 50 ~ 1000 Pa), temperature is 600 ~ 1800 DEG C (preferably 800 ~ 1600 DEG C, more preferably 850 ~ 1300 DEG C); Be 1: 10 ~ 10: 1(preferably 1 ~ 5: 1 ~ 6 according to the throughput ratio of carrier gas and carrier gas, more preferably 1 ~ 2: 1 ~ 3) carrier gas and carrier gas is imported, gas by boron, nitrogen-atoms ratio be 1: 1 single constituent element precursor boron azine bring in deposition burner hearth, boron azine decomposites boron nitride and is deposited on carbon nano tube surface in cvd furnace; Depositing time is 5 ~ 60min(preferably 8 ~ 40 min, more preferably 10 ~ 30 min);
3), after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace;
4) mixture of boron nitride and carbon nanotube is placed in the High Temperature Furnaces Heating Apparatus that retort furnace maybe can pass into oxygen, be warming up to 500 ~ 800 DEG C (preferably 600 ~ 700 DEG C, more preferably 620 ~ 680 DEG C), be incubated 1 ~ 60 hour (preferably 15 ~ 50 hours, more preferably 20 ~ 40 hours), oxidation removal carbon, namely obtains boron nitride nano-tube.
Further, in step 1), described organic solvent is acetone or alcohol.
Further, described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Described carbon nanotube goes deimpurity chemical equation to be by oxidizing reaction:
C+O
2=CO
2, or 2C+O
2=2CO.
Further, described carrier gas can be nitrogen, argon gas, helium or hydrogen, preferred nitrogen.
Further, described carrier gas can be nitrogen, argon gas, helium, hydrogen or ammonia, preferred argon gas.
Research shows, boron azine is the isoelectronic species of benzene, its structure and benzene similar, be therefore also called inorganic benzene, molecular formula is B
3h
6n
3.There is conjugatedπbond in molecule, boron atom and nitrogen-atoms form borazole structure alternately, six atoms respectively connect a hydrogen atom.The six-membered ring structure of boron azine is the basic structural unit of hexagonal boron nitride, and B:N atomic ratio is 1:1, and impurity element containing protium, is only the desirable precursor preparing boron nitride ceramics.
The beneficial effect that the present invention compared with prior art has: with boron azine for single constituent element precursor, chemical vapor deposition method is utilized to prepare boron nitride nano-tube, by means of only the flow controlling deposition burner hearth vacuum tightness, depositing temperature, carrier gas and carrier gas, to meet different application demands, technique is simple, easy to operate, de-carbon does not introduce other impurity elements outward; And carbon can carry out oxidation removal in air or oxygen, thus the boron nitride nano-tube of purity >=98% can be obtained; Meanwhile, by adopting the template carbon nanotube of different size, the size of boron nitride nano-tube, caliber etc. can be controlled.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the boron nitride nano-tube of embodiment 1 gained;
Fig. 2 is the stereoscan photograph of the boron nitride nano-tube microscopic appearance of embodiment 2 gained.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) Single Walled Carbon Nanotube is placed in acetone ultrasonic cleaning, removes surface contaminant, in the vacuum drying oven that temperature is 120 DEG C, put into tube-type chemical vapour deposition burner hearth after abundant drying;
2) 50Pa is evacuated to deposition burner hearth, is warming up to 850 DEG C; Nitrogen buffer gas, argon gas is carrier gas, the throughput ratio of nitrogen and argon gas is 1: 1, the boron azine that boron, nitrogen-atoms ratio are 1: 1 by the mode of bubbling by gas is brought in deposition burner hearth, the boron nitride that boron azine decomposites in deposition burner hearth is deposited on carbon nano tube surface, and depositing time is 30min.
3), after deposition terminates, stop importing nitrogen and argon gas, close heating system, cool to room temperature with the furnace;
4) mixture of boron nitride and carbon nanotube is placed in retort furnace, is warming up to 620 DEG C, be incubated 40 hours, oxidation removal carbon nanotube wherein, namely obtain the boron nitride nano-tube that purity is 99.30%.
The Raman spectrogram of boron nitride nano-tube is visible as shown in Figure 1, is positioned at 1375cm
-1spike be the characteristic peak of boron nitride (h-BN), this confirms further, and product is boron nitride nano-tube.
Embodiment 2
1) multi-walled carbon nano-tubes is placed in acetone ultrasonic cleaning, removes surface contaminant, in the common loft drier that temperature is 150 DEG C, put into vertical chemical vapor deposition stove thorax after abundant drying;
2) 1000Pa is evacuated to deposition burner hearth, is warming up to 1300 DEG C;
3) nitrogen buffer gas, hydrogen is carrier gas, the throughput ratio of nitrogen and hydrogen is 2: 1, the boron azine that boron, nitrogen-atoms ratio are 1: 1 by the mode of bubbling by gas is brought in deposition burner hearth, the boron nitride that boron azine decomposites in deposition burner hearth is deposited on carbon nano tube surface, and depositing time is 20min.
4), after deposition terminates, stop importing nitrogen and hydrogen, close heating system, cool to room temperature with the furnace;
5) mixture of boron nitride and carbon nanotube is placed in tube furnace, continues to pass into oxygen, be warming up to 650 DEG C, be incubated 25 hours, oxidation removal carbon nanotube wherein, namely obtain the boron nitride nano-tube that purity is 98.64%.
The boron nitride nano-tube microscopic appearance of the present embodiment gained as shown in Figure 2.
Embodiment 3
1) multi-walled carbon nano-tubes is placed in acetone ultrasonic cleaning, removes surface contaminant, in the common loft drier that temperature is 200 DEG C, put into vertical chemical vapor deposition stove thorax after abundant drying;
2) 500Pa is evacuated to deposition burner hearth, is warming up to 1600 DEG C;
3) nitrogen buffer gas, hydrogen is carrier gas, the throughput ratio of nitrogen and hydrogen is 1: 3, the boron azine that boron, nitrogen-atoms ratio are 1: 1 by the mode of bubbling by gas is brought in deposition burner hearth, the boron nitride that boron azine decomposites in deposition burner hearth is deposited on carbon nano tube surface, and depositing time is 10min.
4), after deposition terminates, stop importing nitrogen and hydrogen, close heating system, cool to room temperature with the furnace;
5) mixture of boron nitride and carbon nanotube is placed in tube furnace, continues to pass into oxygen, be warming up to 680 DEG C, be incubated 20 hours, oxidation removal carbon nanotube wherein, namely obtains the boron nitride nano-tube of purity 98.17%.
Embodiment 4
1) Single Walled Carbon Nanotube is placed in acetone ultrasonic cleaning, removes surface contaminant, in the vacuum drying oven that temperature is 150 DEG C, put into tube-type chemical vapour deposition burner hearth after abundant drying;
2) 1800Pa is evacuated to deposition burner hearth, is warming up to 790 DEG C;
3) nitrogen buffer gas, hydrogen is carrier gas, and the two throughput ratio is 1:10, and the boron azine that boron, nitrogen-atoms ratio are 1: 1 by the mode of bubbling by gas is brought in deposition burner hearth, the boron nitride that boron azine decomposites in deposition burner hearth is deposited on carbon nano tube surface, and depositing time is 6min.
4), after deposition terminates, stop importing nitrogen and hydrogen, close heating system, cool to room temperature with the furnace;
5) mixture of boron nitride and carbon nanotube is placed in retort furnace, is warming up to 770 DEG C, be incubated 5 hours, oxidation removal carbon nanotube wherein, namely obtains the boron nitride nano-tube of purity 98.45%.
Embodiment 4
1) multi-walled carbon nano-tubes is placed in acetone ultrasonic cleaning, removes surface contaminant, in the vacuum drying oven that temperature is 150 DEG C, put into tube-type chemical vapour deposition burner hearth after abundant drying;
2) 0.1Pa is evacuated to deposition burner hearth, is warming up to 1700 DEG C;
3) nitrogen buffer gas, hydrogen is carrier gas, and the two throughput ratio is 10: 1, and the boron azine that boron, nitrogen-atoms ratio are 1: 1 by the mode of bubbling by gas is brought in deposition burner hearth, the boron nitride that boron azine decomposites in deposition burner hearth is deposited on carbon nano tube surface, and depositing time is 50min.
4), after deposition terminates, stop importing nitrogen and hydrogen, close heating system, cool to room temperature with the furnace;
5) mixture of boron nitride and carbon nanotube is placed in tube furnace, continues to pass into oxygen, be warming up to 550 DEG C, be incubated 60 hours, oxidation removal carbon nanotube wherein, namely obtains the boron nitride nano-tube of purity 98.08%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, obviously, those skilled in the art can carry out various change modification to the present invention and not depart from the spirit and scope of the present invention.If belong within the scope of the claims in the present invention and equivalent technologies thereof these amendments of the present invention and modification, all belong to protection scope of the present invention.
Claims (12)
1. the preparation method of a boron nitride nano-tube, it is characterized in that, in chemical vapor deposition stove, take carbon nanotube as template, with carrier gas and carrier gas, single constituent element precursor boron azine is brought in deposition burner hearth, make boron azine in cvd furnace, decomposite boron nitride and be deposited on carbon nano tube surface; Through oxidation removal carbon, namely obtain boron nitride nano-tube;
Specifically comprise the following steps:
1) carbon nanotube is placed in organic solvent for ultrasonic cleaning, removes surface contaminant, after drying, put into chemical vapor deposition stove thorax;
2) vacuum tightness controlling cvd furnace is 0.01 ~ 2000Pa, and temperature is 600 ~ 1800 DEG C; Be 1: 10 ~ 10: 1 according to the throughput ratio of carrier gas and carrier gas, import carrier gas and carrier gas, gas by boron, nitrogen-atoms ratio be 1: 1 single constituent element precursor boron azine bring in deposition burner hearth, boron azine decomposites boron nitride and is deposited on carbon nano tube surface in cvd furnace; Depositing time is 5 ~ 60min;
3), after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace;
4) mixture of boron nitride and carbon nanotube is placed in the High Temperature Furnaces Heating Apparatus that retort furnace maybe can pass into oxygen, is warming up to 500 ~ 800 DEG C, be incubated 1 ~ 60 hour, oxidation removal carbon, namely obtains boron nitride nano-tube.
2. the preparation method of boron nitride nano-tube according to claim 1, it is characterized in that, in step 1), described organic solvent is acetone or alcohol.
3. the preparation method of boron nitride nano-tube according to claim 1, is characterized in that, step 2) in, the vacuum tightness controlling cvd furnace is 1 ~ 1200Pa, and the temperature controlling cvd furnace is 800 ~ 1600 DEG C, and the throughput ratio of described carrier gas and carrier gas is 1 ~ 5: 1 ~ 6.
4. the preparation method of boron nitride nano-tube according to claim 3, it is characterized in that, described vacuum tightness is 20 ~ 1100 Pa; Described temperature is 850 ~ 1300 DEG C; The throughput ratio of carrier gas and carrier gas is 1 ~ 2: 1 ~ 3.
5. the preparation method of boron nitride nano-tube according to claim 4, it is characterized in that, described vacuum tightness is 50 ~ 1000 Pa.
6., according to the preparation method of the described boron nitride nano-tube of one of Claims 1 to 5, it is characterized in that, step 2) in, described depositing time is 8 ~ 40 min.
7. the preparation method of boron nitride nano-tube according to claim 6, it is characterized in that, described depositing time is 10 ~ 30 min.
8. according to the preparation method of the described boron nitride nano-tube of one of Claims 1 to 5, it is characterized in that, in step 4), the temperature of oxidation removal carbon is 600 ~ 700 DEG C; Soaking time is 15 ~ 50 hours.
9. the preparation method of boron nitride nano-tube according to claim 8, it is characterized in that, the temperature of described oxidation removal carbon is 620 ~ 680 DEG C, and described soaking time is 20 ~ 40 hours.
10. according to the preparation method of the described boron nitride nano-tube of one of Claims 1 to 5, it is characterized in that, described carrier gas is nitrogen, argon gas, helium or hydrogen; Described carrier gas is nitrogen, argon gas, helium, hydrogen or ammonia; Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
The preparation method of 11. boron nitride nano-tubes according to claim 6, it is characterized in that, described carrier gas is nitrogen, argon gas, helium or hydrogen; Described carrier gas is nitrogen, argon gas, helium, hydrogen or ammonia; Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
The preparation method of 12. boron nitride nano-tubes according to claim 8, it is characterized in that, described carrier gas is nitrogen, argon gas, helium or hydrogen; Described carrier gas is nitrogen, argon gas, helium, hydrogen or ammonia; Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
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| JP6411952B2 (en) * | 2015-06-09 | 2018-10-24 | 信越化学工業株式会社 | Method for producing pyrolytic boron nitride container |
| CN107522175A (en) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | A kind of method that solvent dispersion method prepares boron nitride nano-tube |
| CN107265416A (en) * | 2017-06-08 | 2017-10-20 | 中国人民解放军国防科学技术大学 | The preparation method of pyrolytic boron nitride material |
| CN109706550B (en) * | 2019-01-14 | 2021-03-23 | 中原工学院 | Method for preparing hexagonal boron nitride by using carbon nanofibers as template |
| CN116143083B (en) * | 2023-02-02 | 2024-07-05 | 浙江硼矩新材料科技有限公司 | Floating catalytic preparation method of boron nitride nanotube |
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| CN101348242A (en) * | 2008-09-05 | 2009-01-21 | 北京工业大学 | Method for preparing boron nitride nanotube by magnesium reduction |
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