CN114408879A - Hexagonal boron nitride nanotube and preparation method thereof - Google Patents
Hexagonal boron nitride nanotube and preparation method thereof Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 49
- 239000002071 nanotube Substances 0.000 title claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 100
- 229910052742 iron Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000002344 surface layer Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 12
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- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0641—Preparation by direct nitridation of elemental boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
Abstract
The invention relates to a hexagonal boron nitride nanotube and a preparation method thereof. The preparation method comprises the following steps: powder preparation: ball-milling the raw material containing boron powder into powder in nitrogen or ammonia; pulping: mixing the powder with a solvent in nitrogen to obtain slurry; a matrix preparation step: spraying the slurry on the surface of a base material in nitrogen to obtain a matrix; a heat treatment step: a plurality of matrixes are sequentially conveyed into a high-temperature device for heat treatment, the heat-treated matrixes are sequentially output for cooling, continuous heat treatment is realized, and the continuous heat treatment is carried out in ammonia gas or mixed gas of nitrogen gas and hydrogen gas to obtain the matrix on which the hexagonal boron nitride nanotube grows; a collection and purification step: and collecting the hexagonal boron nitride nanotubes grown on the matrix, and purifying and drying to obtain the hexagonal boron nitride nanotubes. The preparation method of the invention does not generate the hexagonal boron nitride nanotube only on the surface layer of the powder, so that the raw materials are fully utilized and the hexagonal boron nitride nanotube with good appearance is obtained.
Description
Technical Field
The invention relates to the field of materials, in particular to a hexagonal boron nitride nanotube and a preparation method thereof.
Background
The hexagonal boron nitride nanotube has excellent mechanical strength, chemical corrosion resistance, high temperature stability and thermal shock resistance. Therefore, the hexagonal boron nitride can be used for manufacturing cutters, molds, insulating and heat-conducting materials, nanoscale electronic devices, nanostructured ceramics, high-strength fibers, high-temperature ultralight wear-resistant protective materials and the like.
The recent cooperation of the National Aviation and Space Administration (NASA) and the university of BingHanton in America proves that the hexagonal boron nitride nanotube can be used as a coating material for the shell of the hypersonic aircraft, and the hexagonal boron nitride nanotube is more widely concerned after the hypersonic aircraft flies at the speed of more than 5 times of the sound speed.
At present, the preparation method of the hexagonal boron nitride nanotube mainly comprises an electric arc discharge method, a laser ablation method, a ball milling annealing method, a carbon nanotube replacement method, a Chemical Vapor Deposition (CVD) method, a solvothermal method, a self-propagating heat treatment-CVD method and the like.
Wherein, the profound research is carried out on the ball grinding annealing method by professor ying in national university of Australia, the core steps are: firstly, grinding boron powder in ammonia gas, and then annealing in nitrogen gas to form the boron nitride nanotube.
However, when the method is used for preparing a small amount or micro-scale boron nitride nanotube in a laboratory, the product has good appearance and performance, and all raw materials can be reacted completely; however, when the boron powder is subjected to the industrial production of a lot of over kilogram level, boron nitride carbon nanotubes can be formed only on the surface layer of the boron powder and no reaction occurs inside the boron powder because the boron powder is large in amount (over kilogram level) when the boron powder after grinding is annealed.
On the basis of the above technical problem, the applicant provides a method for preparing boron nitride nanotubes in batches, so as to solve the technical problem.
Disclosure of Invention
The invention provides a preparation method of a hexagonal boron nitride nanotube, which solves the technical problem that in the prior art, when the boron nitride nanotube is produced in batch, the boron nitride nanotube is generated only on the surface layer by adopting direct heat treatment after being ball-milled into powder and cannot be completely generated.
According to an aspect of the present invention, there is provided a method for preparing hexagonal boron nitride nanotubes, comprising:
powder preparation: ball-milling the raw material containing boron powder into powder in nitrogen or ammonia;
pulping: mixing the powder with a solvent in nitrogen to obtain slurry;
a matrix preparation step: spraying the slurry on the surface of a base material in nitrogen to obtain a matrix;
a heat treatment step: the matrix is a plurality of matrixes, the matrixes are sequentially conveyed into a high-temperature device for heat treatment, the heat-treated matrixes are sequentially output for cooling, continuous heat treatment is realized, and the continuous heat treatment is carried out in ammonia gas or mixed gas of nitrogen gas and hydrogen gas to obtain the matrix on which the hexagonal boron nitride nanotube grows;
a collection and purification step: and collecting the hexagonal boron nitride nanotubes grown on the matrix, and purifying and drying to obtain the hexagonal boron nitride nanotubes.
According to the preparation method of the invention, in the milling step, the raw materials further comprise iron powder.
According to the preparation method, in the powder preparation step, the mass ratio of the boron powder to the iron powder is 999: 1-990: 10;
preferably, the particle size of the iron powder is 10-200 nm.
According to the preparation method of the invention, in the pulping step, the solvent is absolute ethyl alcohol or acetone.
According to the preparation method, in the pulping step, the mass volume ratio of the powder to the solvent is 1g:2 ml-1: 20 ml.
According to the preparation method of the present invention, in the base body preparation step, the base material is an iron sheet or an iron wire mesh;
preferably, the length of the iron sheet is 50-300 cm, the width of the iron sheet is 10-50 cm, and the thickness of the iron sheet is 100-1000 um;
preferably, the length of the iron wire net is 50-300 cm, the width of the iron wire net is 10-50 cm, and the mesh number of the iron wire net is 20-325 meshes.
According to the preparation method, the iron sheet or the iron wire mesh is treated by hydrochloric acid with the mass percentage concentration of 1-10%.
According to the preparation method, in the preparation step of the base body, the thickness of the slurry sprayed to the surface of the base material is 10-1000 um.
According to the preparation method, in the preparation step of the matrix, the spraying pressure is 0.1-0.5 Mpa.
According to another aspect of the invention, a hexagonal boron nitride nanotube is provided, which is prepared by the method of the invention.
Compared with the prior art, the preparation method has the advantages that the powder is pulped and sprayed to the base material to form the matrix, the matrixes are sequentially conveyed to the high-temperature device, and are sequentially output and cooled after heat treatment, so that the phenomenon that the hexagonal boron nitride nanotube is only generated on the surface layer of the powder is avoided, raw materials are fully utilized, kilogram-level batch production is realized, and the hexagonal boron nitride nanotube with good appearance is obtained.
Drawings
FIG. 1 shows a photograph of hexagonal boron nitride nanotubes grown on a wire mesh substrate according to example 1 of the present invention;
FIG. 2 shows an electron micrograph of hexagonal boron nitride nanotubes obtained in example 1 of the present invention;
FIG. 3 shows an electron micrograph of hexagonal boron nitride nanotubes obtained in comparative example 1;
FIG. 4 is a photograph showing the formation of hexagonal boron nitride nanotubes only on the surface layer of the powder obtained in comparative example 2;
fig. 5 shows an electron micrograph and a partial enlarged view of the hexagonal boron nitride nanotubes obtained in comparative example 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the drawings and the embodiments of the specification, and it is obvious that the described embodiments are only a part of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to an aspect of the present invention, there is provided a method for preparing hexagonal boron nitride nanotubes, comprising:
powder preparation: ball-milling the raw material containing boron powder into powder in nitrogen or ammonia;
pulping: mixing the powder with a solvent in nitrogen to obtain slurry;
a matrix preparation step: spraying the slurry on the surface of a base material in nitrogen to obtain a matrix;
a heat treatment step: the matrix is a plurality of matrixes, the matrixes are sequentially conveyed into a high-temperature device for heat treatment, the heat-treated matrixes are sequentially output for cooling, continuous heat treatment is realized, and the continuous heat treatment is carried out in ammonia gas or mixed gas of nitrogen gas and hydrogen gas to obtain the matrix on which the hexagonal boron nitride nanotube grows;
a collection and purification step: and collecting the hexagonal boron nitride nanotubes grown on the matrix, and purifying and drying to obtain the hexagonal boron nitride nanotubes.
According to the preparation method, compared with the prior art, after the powder is prepared into slurry and sprayed on the base material to form the matrix, the plurality of matrixes can be sequentially conveyed to the high-temperature device, and are sequentially output for cooling after heat treatment, so that the phenomenon that the hexagonal boron nitride nanotube is only generated on the surface layer of the powder is avoided, the raw materials are fully utilized, kilogram-level batch production is realized, and the hexagonal boron nitride nanotube with good appearance is obtained.
Wherein the temperature of the high temperature apparatus is preferably 900 deg.C, 1000 deg.C, 1100 deg.C, 1200 deg.C, 1300 deg.C, 1400 deg.C, 1500 deg.C and 1600 deg.C.
In the step of collecting and purifying, putting the matrix on which the hexagonal boron nitride nanotubes grow into dilute hydrochloric acid with the mass concentration of 1-10% for ultrasonic treatment, filtering after ultrasonic treatment, and collecting to obtain a master batch; or scraping the hexagonal boron nitride nanotube from the matrix by using a tool and collecting to obtain a master batch; wherein the master batch is a hexagonal boron nitride nanotube containing impurities.
Among them, the concentration of hydrochloric acid is preferably 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10% by mass.
In the step, ultrasonic collection is preferred, on one hand, the hexagonal boron nitride nanotube can be completely removed from the matrix by ultrasonic treatment, and the yield of the hexagonal boron nitride nanotube is improved; on the other hand, the iron sheet or iron wire mesh substrate which is oxidized can be activated by ultrasonic treatment in dilute hydrochloric acid to have catalytic action again, so that the iron sheet or iron wire mesh substrate can be used in the matrix preparation step again.
In the step of collection and purification, the master batch is sequentially washed by distilled water and 75% ethanol, and the washed hexagonal boron nitride nanotube is dried at the temperature of 70-90 ℃ for 2-12 hours to obtain the high-purity hexagonal boron nitride nanotube.
Wherein, preferably, the drying temperature is 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃; the drying time is preferably 2h, 4h, 6h, 8h, 10h and 12 h.
According to the preparation method of the invention, in the powdering step, the raw materials further include iron powder.
The iron powder is added into the raw materials in the invention to play a role of a catalyst, and uniform hexagonal boron nitride nanotubes are generated on a matrix.
According to the preparation method, in the powder preparation step, the mass ratio of boron powder to iron powder is 999: 1-990: 10;
preferably, the particle size of the iron powder is 10-200 nm.
Preferably, the boron powder and the iron powder are calculated by mass ratio as follows: 999:1, 998:2, 997:3, 996:4, 995:5, 994:6, 993:7, 992:8, 991:9 and 990: 10.
Preferably, the particle size of the iron powder is 10 to 200nm, more preferably 50 to 150nm, and still more preferably 80 to 100 nm.
The particle size of the iron powder is between 10nm and 200nm, so that the iron powder has an excellent catalytic effect; when the particle size is less than 10nm, the particle size is not easy to store, and when the particle size is more than 200nm, the particle size is larger, and the catalytic effect is not good.
In the powder preparation step, preferably, boron powder and iron powder are mixed according to a mass ratio of 999: 1-990: 10, ball milling for 2-60 hours in a nitrogen or ammonia environment, wherein a ball milling tank is preferably made of stainless steel, and the ball milling speed is preferably 100-400 r/min.
Wherein, the ball milling time is adjusted according to the amount of the raw materials, and the optimization is as follows: 2h, 4h, 6h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h and 60 h.
According to the preparation method of the invention, in the pulping step, the solvent is absolute ethyl alcohol or acetone.
According to the preparation method, in the pulping step, the mass volume ratio of the powder to the solvent is 1g:2 ml-1 g:20 ml.
Preferably, the mass volume ratio of the powder to the solvent is 1g:2ml, 1g:5ml, 1g:10ml, 1g:15ml, 1g:20 ml.
According to the preparation method of the invention, in the matrix preparation step, the base material is an iron sheet or an iron wire net;
preferably, the length of the iron sheet is 50-300 cm, the width is 10-50 cm, and the thickness is 100-1000 um;
preferably, the wire mesh has a length of 50-300 cm, a width of 10-50 cm and a mesh number of 20-325 meshes.
Wherein the thickness of the iron sheet is further preferably 100um, 200um, 300um, 400um, 500um, 600um, 700um, 800um, 900um and 1000 um; further preferably 10cm, 15cm, 20cm, 25cm, 30cm, 40cm and 50cm in width; further preferred lengths are 50cm, 100cm, 150cm, 200cm, 250cm and 300 cm.
The mesh number of the wire mesh is further preferably 20 meshes, 30 meshes, 50 meshes, 80 meshes, 100 meshes, 150 meshes, 200 meshes, 250 meshes, 300 meshes and 325 meshes; further preferred are widths of 10cm, 15cm, 20cm, 25cm, 30cm, 40cm and 50 cm; further preferred are lengths of 50cm, 100cm, 150cm, 200cm, 250cm and 300 cm.
The iron sheet and the iron wire mesh are used as base materials and can also play a role of a catalyst; the iron sheet and the iron wire mesh are matched with iron powder in the slurry for catalysis to generate the uniform hexagonal boron nitride nanotube.
Due to the adoption of the wire mesh, the contact area between the wire mesh and the slurry is increased due to the existence of the holes, and the hexagonal boron nitride nanotube can be generated more uniformly.
When the mesh number of the iron wire net is 20-325 meshes, a good slurry layer can be formed during spraying, and the contact area can be increased; when the particle size is less than 20 meshes, the particle size is too large to form a slurry layer, and when the particle size is more than 325 meshes, the particle size is too small, so that the growth of the hexagonal boron nitride nanotube is not facilitated, and the pores can be blocked.
According to the preparation method, the iron sheet or the iron wire mesh is treated by hydrochloric acid with the mass percentage concentration of 1-10%.
Among them, the concentration of hydrochloric acid is preferably 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10%.
After the iron sheet or the iron wire mesh is treated by hydrochloric acid, the surface becomes rough, and hollow hexagonal boron nitride nanotube growing points are formed, which is beneficial to the generation of the hexagonal boron nitride nanotube.
According to the preparation method, in the preparation step of the matrix, the thickness of the slurry sprayed to the surface of the base material is 10-1000 um.
When the thickness of the slurry is less than 10um, the amount of the slurry borne by the matrix is too small, the yield of the generated hexagonal boron nitride nanotube is low, when the thickness of the slurry is more than 1000um, the hexagonal boron nitride nanotube may not be generated at the bottom layer, and if the base material is an iron wire net, the pores are easily blocked, which is not beneficial to the growth of the hexagonal boron nitride nanotube. Therefore, when the thickness is 10-1000 um, a large amount of uniform hexagonal boron nitride nanotubes can be generated, the pores can not be blocked, and the phenomenon that the hexagonal boron nitride nanotubes are not generated on the bottom layer is avoided.
Further preferably, the thickness of the slurry is 10um, 30um, 50um, 80um, 100um, 200um, 300um, 400um, 500um, 600um, 700um, 800um, 900um and 1000 um.
According to the preparation method, in the preparation step of the matrix, the spraying pressure is 0.1-0.5 Mpa.
Further preferably, the spraying pressure is 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa and 0.5 MPa.
In the matrix preparation step, preferably, the slurry is uniformly sprayed on the surface of the iron sheet or the iron wire mesh cleaned by dilute hydrochloric acid by using a spray gun under the protection of nitrogen.
Preferably, according to the preparation method provided by the invention, in the heat treatment step, the matrixes are sequentially conveyed to a JY-IV-2000 high-temperature device with the temperature of 900-1600 ℃, and are subjected to heat treatment for 2 min-20 h under the protection of nitrogen or mixed gas of hydrogen/nitrogen (3/17 v/v).
According to another aspect of the invention, a hexagonal boron nitride nanotube is provided, which is prepared by the method of the invention.
The hexagonal boron nitride nanotube is of a bamboo-like or through-hole structure, the diameter of the hexagonal boron nitride nanotube is 50 nm-2 um, and the length of the hexagonal boron nitride nanotube is 100 nm-1 cm.
In order to better illustrate the technical solution of the present invention, the present invention will be further described with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the present invention.
Example 1
Firstly, the step of milling powder is carried out: boron powder and iron powder are mixed according to the mass ratio of 998:2 (wherein, 998g of boron powder and 2g of iron powder) are evenly placed in four 500ml stainless steel ball milling tanks, nitrogen is filled for protection, the ball milling speed is 350r/min, and the ball milling is carried out for 30 hours, so as to obtain powder;
then, the pulping step is carried out: dispersing the powder in absolute ethyl alcohol under a nitrogen environment to obtain slurry, wherein the mass volume ratio of the ball-milled powder to the absolute ethyl alcohol is 1g:10 ml;
then, a matrix preparation step is carried out: transferring the slurry to a spray gun under the nitrogen protection environment, and spraying the slurry to a plurality of 325-mesh wire nets cleaned by 2% diluted hydrochloric acid by adopting the spraying pressure of 0.2MPa, wherein the wire nets have the width of about 10cm and the length of about 50cm, and the thickness of the slurry is about 20 mu m;
then, carrying out a heat treatment step: sequentially conveying the matrixes to a JY-IV-2000 high-temperature device preheated to 1200 ℃, and carrying out high-temperature treatment for 20min under the protection of mixed gas of hydrogen/nitrogen (3/17 v/v); outputting the iron sheet after heat treatment under the protection of nitrogen, and slowly cooling to room temperature;
and finally, carrying out a collection and purification step: putting the matrix on which the hexagonal boron nitride nanotube grows in dilute hydrochloric acid with the mass concentration of 5% for ultrasonic treatment, filtering and collecting after ultrasonic treatment to obtain a master batch;
washing the master batch with distilled water and 75% ethanol in sequence, and drying the washed white powder in air at 80 ℃ for 4 hours to obtain the hexagonal boron nitride nanotube.
The purity of the hexagonal boron nitride nanotubes obtained was about 80%, the weight was 0.5 kg (500g), and the yield was 50%.
Example 2
The conditions of example 2 and example 1 were the same except that the slurry thickness was about 300 um.
The purity of the hexagonal boron nitride nanotubes obtained was about 82%, the weight was 490g, and the yield was 49%.
Example 3
Example 3 was the same as example 1 except that the slurry thickness was about 800 um.
The purity of the obtained hexagonal boron nitride nanotubes was about 81%, the weight was 510g, and the yield was 51%.
Comparative example 1
Comparative example 1 no pulping and matrix preparation steps were performed, heat treatment was directly performed after powdering; the powder preparation step was carried out under exactly the same conditions as in example 1 except that the amounts of boron powder and iron powder were 998mg and 2mg, respectively; the heat treatment temperature and time were exactly the same as in example 1.
In comparative example 1, 500mg of boron nitride nanotubes with a purity of 80% were obtained, and the yield could reach 50%.
Comparative example 2
In comparative example 2, the conditions were the same as in comparative example 1 except that the boron powder and the iron powder were used in the same amounts as in example 1.
In comparative example 2, boron nitride nanotubes were formed only on the surface layer of the powder after the heat treatment, and hexagonal boron nitride nanotubes were formed only in a very small amount with respect to the raw material, and thus no purification was performed and no yield calculation was performed.
As shown in the photograph of fig. 1, the uniform white substance was formed on the surface of the wire gauze after the temperature was slowly decreased in example 1, and it was found that all of the slurry sprayed on the wire gauze produced hexagonal boron nitride nanotubes.
As shown in the electron micrograph of fig. 2, uniform hexagonal boron nitride nanotubes were produced in example 1.
Applicants also characterized the small amount of hexagonal boron nitride produced in gram scale in comparative example 1 by electron microscopy, as shown in particular in fig. 3.
From a comparison of the electron micrographs of fig. 3 and 2, it can be seen that: the appearance of the kilogram-grade batch-produced hexagonal boron nitride nanotubes prepared by the preparation method is as good as that of the kilogram-grade micro-prepared hexagonal boron nitride nanotubes.
FIG. 4 is a photograph of the heat-treated sample of comparative example 2, in which only a thin layer of white powder was observed on the surface of the sample and the inside was black material.
As can also be seen from fig. 5, in example 2, only one layer of hexagonal boron nitride nanotubes is grown on the surface, and the bottom is used as the raw material.
Comparing fig. 1 and fig. 4, and comparing fig. 2 and fig. 5, it can be seen that the preparation method of the present invention solves the problem that in the prior art, when a kilogram-level product is prepared, only the hexagonal boron nitride nanotube is formed on the surface layer, and mass production cannot be performed.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for preparing hexagonal boron nitride nanotubes is characterized by comprising the following steps:
powder preparation: ball-milling the raw material containing boron powder into powder in nitrogen or ammonia;
pulping: mixing the powder with a solvent in nitrogen to obtain slurry;
a matrix preparation step: spraying the slurry on the surface of a base material in nitrogen to obtain a matrix;
a heat treatment step: the matrix is a plurality of matrixes, the matrixes are sequentially conveyed into a high-temperature device for heat treatment, the heat-treated matrixes are sequentially output for cooling, continuous heat treatment is realized, and the continuous heat treatment is carried out in ammonia gas or mixed gas of nitrogen gas and hydrogen gas to obtain the matrix on which the hexagonal boron nitride nanotube grows;
a collection and purification step: and collecting the hexagonal boron nitride nanotubes grown on the matrix, and purifying and drying to obtain the hexagonal boron nitride nanotubes.
2. The method according to claim 1, wherein in the powdering step, the raw material further includes iron powder.
3. The method according to claim 2, wherein, in the step of pulverizing,
the mass ratio of the boron powder to the iron powder is 999: 1-990: 10;
preferably, the particle size of the iron powder is 10-200 nm.
4. The method according to claim 1, wherein in the pulping step, the solvent is absolute ethanol or acetone.
5. The preparation method according to claim 4, wherein in the pulping step, the mass-to-volume ratio of the powder to the solvent is 1g:2ml to 1g:20 ml.
6. The method according to claim 1, wherein in the base body preparation step, the base material is an iron sheet or an iron wire;
preferably, the length of the iron sheet is 50-300 cm, the width of the iron sheet is 10-50 cm, and the thickness of the iron sheet is 100-1000 um;
preferably, the length of the iron wire net is 50-300 cm, the width of the iron wire net is 10-50 cm, and the mesh number of the iron wire net is 20-325 meshes.
7. The method according to claim 6, wherein the iron sheet or wire is treated with hydrochloric acid having a concentration of 1 to 10% by mass.
8. The method according to claim 1, wherein in the base preparation step, the thickness of the slurry sprayed onto the surface of the base material is 10 to 1000 um.
9. The method according to claim 8, wherein in the substrate preparation step, the spraying pressure is 0.1 to 0.5 Mpa.
10. A hexagonal boron nitride nanotube characterized by being prepared by the method of any one of claims 1 to 8.
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