CN105036096B - A kind of method that utilization reacting gas vortex prepares high-purity boron nitride nano-tube - Google Patents
A kind of method that utilization reacting gas vortex prepares high-purity boron nitride nano-tube Download PDFInfo
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Abstract
Be vortexed the method for preparing high-purity boron nitride nano-tube the invention discloses a kind of utilization reacting gas, and its step is as follows：First, take unformed boron powder to be mixed with nine water ferric nitrates, mixed-powder is put into ball milling in vacuum ball grinder；2nd, horizontal sintering furnace heating；3rd, the mixed-powder that ball milling is completed is taken out in glove box, mixed-powder is put into bottle and adds absolute ethyl alcohol for being fabricated to boron dope, is used after ultrasonic disperse；4th, boron dope brush on steel plate substrate and is put into nitrogen hydrogen mixeding gas vortex generating means, in the sintering furnace for placing a device into horizontal positioned, the opening of nitrogen hydrogen mixeding gas vortex generating means is towards air inlet；5th, using N2+ 15%H2Atmosphere is annealed, and boron nitride nano-tube is obtained on substrate.This method is economic and practical, and the boron nitride nano-tube chemistry and heat endurance produced are good, and part can go out boron nitride nano-tube along the direction oriented growth of cyclone, with very high scientific research value.
Description
Technical field
It is specially that one kind is vortexed to manufacture using reacting gas the present invention relates to a kind of synthetic method of boron nitride nano-tube
The method of high-purity boron nitride nano-tube.
Background technology
Boron nitride nano-tube is emerging nano material, is typical wide bandgap semiconductor nano-electron material, and its forbidden band is wide
Degree is in 5.5ev；It has good mechanical performance, thermal property and excellent hydrophobic performance, is studied with further, its
Application prospect is very fine, such as ceramics, the high strength fibre material of electronic device, nanostructured available for manufacture nanoscale
Material；The fixation property of boron nitride nano-tube surface ferritin is in potential medical treatment and nano meter biomaterial application；Boron nitride nanometer
Pipe shows weaker superparamagnetism, available for nanometer micro-magnetic device；In addition, compared with CNT, entering after carbon doping
Boron nitride nano-tube there is more stable high temperature resistant and chemically stable property, can be applicable to the Flied emission such as flat-panel monitor
Device, scanning tunneling microscope (STM) and atomic force SEM (AFM) top emission part etc..
Gas swirl is sometimes referred to as gas swirl, refers to that a kind of cylinder of radius very little rotates in stationary fluid and causes week
The compact district for having a vorticity inside the flow phenomenon that fluid is circled, general vortex, referred to as vortex core are enclosed, it moves similar firm
Body rotates, and speed is directly proportional to radius.In its outside, peripheral speed and the radius of fluid are inversely proportional.And gas swirl also has
One characteristic is exactly that the pressure of whirlpool body will be far longer than outside vortex core and whirlpool.By to boron nitride nano-tube manufacturing process
Further investigation, find in the subrange of air whirl, reacting gas air pressure increase, be conducive to the boron nitride of high-purity to receive
The growth of mitron, wherein gas swirl can be by controlling the flow direction of gas come artificial manufacture.
Recent years, the synthetic method of many synthesis boron nitride nano-tubes is occurred in that, main preparation method mainly has
Arc discharge method, laser ablation method, mechanical attrition method, CNT displacement method, chemical vapour deposition technique, template etc., wherein
Mechanical ball mill annealing method is method that is a kind of simple and efficiently manufacturing boron nitride nano-tube.
The content of the invention
Be vortexed the method for preparing high-purity boron nitride nano-tube it is an object of the invention to provide a kind of utilization reacting gas, with
Based on mechanical ball mill annealing method, reacting gas whirlpool is produced by building a gas swirl device, nitrogen is further improved
Change the yield and purity of boron nanotube.This method is economic and practical, and the boron nitride nano-tube produced is chemical and thermally-stabilised
Property it is good, and it is local can go out boron nitride nano-tube along the direction oriented growth of cyclone, with very high scientific research value.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that utilization reacting gas vortex prepares high-purity boron nitride nano-tube, first using nitrogen hydrogen whirlpool
Rotation, its generation device is applied and spreads the stainless steel substrate of boron source and be put into sintering boat to be that sintering boat is put into cylindrical crucible, circle
The opening of skittele pot will produce nitrogen so when nitrogen gas are passed through towards air inlet near crucible interior substrate
Hydrogen is vortexed.Aerochemistry key is unfolded into nitrogen hydrogen plasma vortex under the high temperature conditions, and scroll body can form part
The growth of substrate surface boron nitride nano-tube is greatly facilitated in high pressure, the nitrogen hydrogen plasma of high pressure.Comprise the following steps that：
First, unformed boron powder and nine water ferric nitrates are taken by 25:Mixed-powder is put into vacuum sphere by 1~3 weight than mixing
Nitrogen or nitrogen and hydrogen gas mixture are passed through in grinding jar, in tank, and (mixed volume ratio is 20:3) atmospheric pressure, after sealing
Ball milling 6~18 hours；
2nd, horizontal sintering furnace is warming up to 1050~1150 DEG C；
3rd, the mixed-powder that ball milling is completed is taken out in glove box, mixed-powder is put into bottle and adds absolute ethyl alcohol
For being fabricated to boron dope, used after ultrasonic disperse, wherein the ratio of mixed-powder and absolute ethyl alcohol is 1: 0.1~0.6ml；
4th, boron dope brush on steel plate substrate and is put into nitrogen hydrogen mixeding gas vortex generating means, device is put
In the sintering furnace for entering horizontal positioned, the opening of nitrogen hydrogen mixeding gas vortex generating means is towards air inlet, and substrate is 2.5CM*1CM
Stainless steel substrate, surfacing is smooth；
5th, using N2+ 15%H2Atmosphere is annealed, and furnace gas flow is in 0.2~0.6ml/min, when being passed through gas
When, device inside can cause substrate surface to form micro- nitrogen hydrogen mixeding gas plasma flow vortex, promote the nitrogen of high-purity
Change the generation of boron nanotube, as shown in figure 3, and can generate in the horizontal direction along etc. particle body gas swirl direction oriented growth
Boron nitride nano-tube.
The present invention has the advantages that：
The present invention has found that micro- reacting gas is vortexed to produce by research and having for boron nitride nano-tube is promoted to make first
With, promote the growth of the boron nitride nano-tube of high-purity by using gas swirl generation device on the basis of this, its
The boron nitride nano-tube of growth is many walls nanotube of Bamboo-shaped, and with very high purity, purity is in 97% or so (Fig. 5)；And
The boron nitride nanometer that the regional area of substrate can form oriented growth along gas swirl direction restrains (Fig. 1).And boron nitride
The length of nanotube is very long, typically in 5um~100um or so, and diameter is typically at 30~250nm (Fig. 4), chemical stability,
Thermally-stabilised very good, impurity is few, and is easy to the follow-up separation of purification, with very high scientific research and commercial value.
Brief description of the drawings
Fig. 1 is the schematic diagram of nitrogen hydrogen mixeding gas vortex generating means, and 11 be cylindrical type silica crucible, representated by 12
It is stainless steel or refractory metal substrate for boat type silica crucible, 13；
Fig. 2 is to planing surface schematic diagram on front side of the comsol of nitrogen hydrogen vortex generating means；
Fig. 3 is the boron nitride nano-tube grown along air-flow vortex direction；
Fig. 4 schemes for the SEM of high-purity boron nitride nano-tube；
Fig. 5 is the EDS results of boron nitride nano-tube；
Fig. 6 is boron nitride nano-tube pictorial diagram.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this
Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should be covered
In protection scope of the present invention.
Embodiment 1
(1) by boron oxide and nine water ferric nitrates according to weight ratio 25：2 mixing, are placed in Stainless Steel Vacuum ball grinder, ball milling
Taken out after 6 hours, obtain well mixed solid powder.
(2) horizontal sintering furnace heats up in nitrogen atmosphere, and heating rate is 5 DEG C per minute, and gas flow rate is 4 milliliters/it is every
Minute, temperature rises to 1150 DEG C.
(3) by the solid powder obtained in step (1) in glove box according to 1g:10ML ratio, which is put into alcohol, to be modulated into
Boron dope.
(4) boron dope being made is brushed on stainless steel substrate, be then placed in after nitrogen hydrogen vortex generating means, rapidly
It is positioned in horizontal sintering furnace, is open towards air inlet.
(5) after the completion of step (4), sintering furnace is passed through 0.2 milliliter/N per minute2+ 15%H2Mixed gas, insulation is 1 small
Shi Hou, starts progressively to cool to after 500 DEG C, closes gas and cools to room temperature, white solid matter is obtained on substrate, the white
Solid is the boron nitride nano-tube of the Bamboo-shaped of many walls, and material object is as shown in Figure 6.
As shown in Figure 1-2, nitrogen hydrogen mixeding gas vortex generating means is by boat type silica crucible 12 and the quartzy earthenware of cylindrical type
Crucible 11 constitute (boat type silica crucible 12 be put into cylindrical type silica crucible 11 be internally located at top position), nitrogen hydrogen mixeding gas from
White arrow direction enters, and runs into stop and forms gas swirl, when by boat type silica crucible 12, collides again, office
Portion forms gas swirl, reaches the effect needed for us.
Tested through EDS, element ratio and purity can be clearly seen in Figure 5, its atomic percent is up to more than 95%.
Scheme (Fig. 4) through SEM and find out that boron nitride nano-tube has an one-dimensional wire pattern, diameter is about length about 5 between 60~200 nanometers
Micron, illustrates that product morphology is homogeneous, and purity is high, and yield is big, and with Bamboo-shaped, and with certain direction of growth, the above
What collection of illustrative plates illustrated that the present invention obtains is, with high-purity boron nitride nano-tube, and to illustrate microcosmic gas swirl to boron nitride
The direction of growth control of nanotube, and the raising of purity have influence.
Embodiment 2
(1) boron oxide and nine water ferric nitrates are mixed according to weight ratio 25: 1, are placed in Stainless Steel Vacuum ball grinder, ball milling
Taken out after 8 hours, obtain well mixed solid powder.
(2) horizontal sintering furnace heats up in nitrogen atmosphere, and heating rate is 8 DEG C per minute, and gas flow rate is 2 milliliters/it is every
Minute, temperature rises to 1100 DEG C.
(3) by the solid powder obtained in step (1) in glove box according to 1g:8ML ratio, which is put into alcohol, to be modulated into
Boron dope.
(4) boron dope being made is brushed on stainless steel substrate, is then placed in sintering boat and the nitrogen of cylindrical crucible formation
After hydrogen vortex generating means, it is positioned over rapidly in horizontal sintering furnace, is open towards air inlet.
(5) after the completion of step (4), sintering furnace is passed through 0.4 milliliter/N per minute2+ 15%H2Mixed gas, insulation 1.5
After hour, start progressively to cool to after 300 DEG C, close gas and cool to room temperature, white solid matter is obtained on substrate, this is white
Color solid is the boron nitride nano-tube of the Bamboo-shaped of many walls.
Embodiment 3
(1) boron oxide and nine water ferric nitrates are mixed according to weight ratio 25: 1, are placed in Stainless Steel Vacuum ball grinder, ball milling
Taken out after 12 hours, obtain well mixed solid powder.
(2) horizontal sintering furnace heats up in nitrogen atmosphere, and heating rate is 10 DEG C per minute, and gas flow rate is 3 milliliters/it is every
Minute, temperature rises to 1050 DEG C.
(3) by the solid powder obtained in step (1) in glove box according to 1g:7ML ratio, which is put into alcohol, to be modulated into
Boron dope.
(4) boron dope being made is brushed on stainless steel substrate, is then placed in sintering boat and the nitrogen of cylindrical crucible formation
After hydrogen vortex generating means, it is positioned over rapidly in horizontal sintering furnace, is open towards air inlet.
(5) after the completion of step (4), sintering furnace is passed through 3 milliliters/N per minute2+ 15%H2Mixed gas, insulation is 1.5 small
Shi Hou, starts progressively to cool to after 200 DEG C, closes gas and cools to room temperature, white solid matter is obtained on substrate, the white
Solid is the boron nitride nano-tube of the Bamboo-shaped of many walls.
Claims (4)
- A kind of method for preparing high-purity boron nitride nano-tube 1. utilization reacting gas is vortexed, it is characterised in that methods described step It is as follows：First, unformed boron powder and nine water ferric nitrates are taken by 25:Mixed-powder is put into vacuum ball grinder by 1 ~ 3 weight than mixing In, nitrogen or nitrogen and one atmospheric pressure of hydrogen gas mixture, ball milling 6 ~ 18 hours after sealing are passed through in tank；2nd, horizontal sintering furnace is warming up to 1050 ~ 1150 DEG C；3rd, the mixed-powder that ball milling is completed is taken out in glove box, mixed-powder is put into bottle and adds alcohol to make Into boron dope, used after ultrasonic disperse, wherein the ratio of mixed-powder and alcohol is 1g：7ml、1g：8ml or 1g：10ml；4th, boron dope brush on steel plate substrate and is put into nitrogen hydrogen mixeding gas vortex generating means, the nitrogen hydrogen mixing Gas swirl generating means is made up of boat type silica crucible with cylindrical type silica crucible, and boat type silica crucible is put into cylindrical type Silica crucible is internally located in top position, the sintering furnace for placing a device into horizontal positioned, and the opening direction of cylindrical crucible is entered Gas port；5th, using N2+15%H2Atmosphere is annealed, and boron nitride nano-tube is obtained on substrate.
- The method for preparing high-purity boron nitride nano-tube, its feature 2. utilization reacting gas according to claim 1 is vortexed It is in the mixed gas, the volume ratio of nitrogen and hydrogen is 20:3.
- The method for preparing high-purity boron nitride nano-tube, its feature 3. utilization reacting gas according to claim 1 is vortexed It is the stainless steel substrate that the substrate is 2.5CM*1CM.
- The method for preparing high-purity boron nitride nano-tube, its feature 4. utilization reacting gas according to claim 1 is vortexed It is the N2+15%H2Flow is in 0.2 ~ 0.6ml/min.
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| CN107522178A (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 for preparing boron nitride nano-tube |
| CN107522180A (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 preparation method of boron nitride nano-tube |
| CN109012903B (en) * | 2018-07-20 | 2020-05-12 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of surface disordered nano material |
| CN109650356A (en) * | 2019-02-27 | 2019-04-19 | 哈尔滨工业大学 | A method of boron nitride nanometer band is prepared using base metal catalysts |
| CN111569530B (en) * | 2020-05-26 | 2021-11-23 | 中国人民解放军火箭军工程大学 | Super-hydrophobic filter screen and preparation method thereof |
| CN114408879A (en) * | 2022-01-31 | 2022-04-29 | 山东晶亿新材料有限公司 | Hexagonal boron nitride nanotube and preparation method thereof |
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| CN102899659A (en) * | 2012-10-16 | 2013-01-30 | 哈尔滨工业大学 | Preparation method of boron nitride nanotube hydrophobic membrane |
| CN102849694A (en) * | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
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