CN116199194B - Preparation method of boron nitride nanotubes and boron nitride nanotubes - Google Patents
Preparation method of boron nitride nanotubes and boron nitride nanotubes Download PDFInfo
- Publication number
- CN116199194B CN116199194B CN202310208969.7A CN202310208969A CN116199194B CN 116199194 B CN116199194 B CN 116199194B CN 202310208969 A CN202310208969 A CN 202310208969A CN 116199194 B CN116199194 B CN 116199194B
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- reactor
- preparation
- nitride nanotubes
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 44
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052796 boron Inorganic materials 0.000 claims abstract description 26
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 23
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052582 BN Inorganic materials 0.000 claims description 64
- 239000002071 nanotube Substances 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- ZZPBMXSWFLVLPM-UHFFFAOYSA-N magnesium potassium borate Chemical compound B([O-])([O-])[O-].[Mg+2].[K+] ZZPBMXSWFLVLPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
本申请公开了一种氮化硼纳米管的制备方法及氮化硼纳米管，制备方法包括称取原料至反应器中，所述原料包括碳酸盐、氧化镁和硼前驱体；将所述反应器在惰性气氛下升温至反应温度，以生成前驱体，所述反应温度为850～1200℃；将所述反应器置于氨气气氛下，保持所述反应温度，持续反应生成氮化硼纳米管；将所述反应器在惰性气氛下冷却至室温，得到氮化硼纳米管。本申请制备方法可在850℃的相对低温下生长氮化硼纳米管，在950℃下即可得到大量高品质氮化硼纳米管，有效降低氮化硼纳米管的合成温度，降低氮化硼纳米管的制备成本，有助于氮化硼纳米管的广泛应用和工业化生产。
The present application discloses a method for preparing boron nitride nanotubes and boron nitride nanotubes, the preparation method comprising weighing raw materials into a reactor, the raw materials comprising carbonate, magnesium oxide and a boron precursor; heating the reactor to a reaction temperature under an inert atmosphere to generate a precursor, the reaction temperature being 850 to 1200°C; placing the reactor under an ammonia atmosphere, maintaining the reaction temperature, and continuously reacting to generate boron nitride nanotubes; cooling the reactor to room temperature under an inert atmosphere to obtain boron nitride nanotubes. The preparation method of the present application can grow boron nitride nanotubes at a relatively low temperature of 850°C, and a large amount of high-quality boron nitride nanotubes can be obtained at 950°C, effectively reducing the synthesis temperature of boron nitride nanotubes, reducing the preparation cost of boron nitride nanotubes, and contributing to the wide application and industrial production of boron nitride nanotubes.
Description
Technical Field
The application belongs to the technical field of nano materials, and particularly relates to a preparation method of a boron nitride nanotube and the boron nitride nanotube.
Background
At present, the preparation method of boron nitride nanotubes (BNT) is mainly divided into an ultrahigh temperature preparation technology and a high temperature preparation technology. The temperature of the ultra-high temperature preparation technology is generally above 2000 ℃, the growth temperature is extremely high, the production cost is extremely high, and the method is not suitable for industrial mass production. The temperature of the high-temperature preparation technology is generally 1100-1500 ℃, wherein Chemical Vapor Deposition (CVD) equipment is simple and easy to control, and the obtained BNNTs is high in quality and is the most favored method. In the current method for preparing BNNTs by CVD, the precursor is the most classical boron and metal oxide, or boron and metal compound, or boride and nitride, and the synthesis temperature of BNNTs is above 1100 ℃ because of the higher melting point, so that the application of CVD preparation BNNTs in industrial production is greatly limited.
Disclosure of Invention
The application aims to provide a preparation method of a boron nitride nanotube and the boron nitride nanotube, which are used for solving the technical problems that the production cost of the boron nitride nanotube is too high and the industrial production of the boron nitride nanotube is limited due to the fact that the synthesis temperature of the boron nitride nanotube is too high in the prior art.
In order to achieve the above purpose, the application adopts a technical scheme that:
A preparation method of the boron nitride nanotube is provided, which comprises the following steps:
Weighing raw materials into a reactor, wherein the raw materials comprise carbonate, magnesium oxide and boron precursors;
heating the reactor to a reaction temperature in an inert atmosphere to generate a precursor, wherein the reaction temperature is 850-1200 ℃;
placing the reactor in ammonia atmosphere, maintaining the reaction temperature, and continuously reacting to generate boron nitride nanotubes;
and cooling the reactor to room temperature under inert atmosphere to obtain the boron nitride nanotube.
In one or more embodiments, the molar ratio of carbonate, magnesium oxide and boron precursor in the raw material is 1:1 (2-6).
In one or more embodiments, the carbonate in the feedstock is one or a combination of two of potassium carbonate and sodium carbonate.
In one or more embodiments, in the step of heating the reactor to a reaction temperature under an inert atmosphere, the heating is specifically heating the reactor at a constant speed of 10-30 ℃ per minute.
In one or more embodiments, in the step of heating the reactor to the reaction temperature under an inert atmosphere, the inert atmosphere is specifically argon gas with a flow rate of 20-100 standard cubic centimeters per minute.
In one or more embodiments, in the step of placing the reactor under an ammonia gas atmosphere, the ammonia gas atmosphere is specifically ammonia gas with a flow rate of 20-100 standard cubic centimeters per minute.
In one or more embodiments, the reaction temperature is 950 ℃ to 1200 ℃.
In one or more embodiments, in the step of generating the boron nitride nanotubes by the continuous reaction, the continuous reaction is specifically a reaction for 60-180 min.
In one or more embodiments, the reactor is a boron nitride boat and the heating is specifically by placing the reactor at a central heating of a tube furnace.
In order to achieve the above object, another technical scheme adopted by the present application is as follows:
The boron nitride nanotube prepared by the preparation method of any embodiment is provided.
Compared with the prior art, the application has the beneficial effects that:
according to the preparation method, the low-melting-point precursor is prepared by using the carbonate, the magnesium oxide and the boron precursor in the heating process, and then the boron nitride nanotube is generated by continuous reaction at a lower temperature, so that the growth temperature can be effectively reduced, the preparation cost of the boron nitride nanotube is reduced, and the wide application and industrial production of the boron nitride nanotube are facilitated;
The preparation method can grow the boron nitride nanotubes at a relatively low temperature of 850 ℃ and can obtain a large amount of high-quality boron nitride nanotubes at 950 ℃, thereby effectively reducing the synthesis temperature of the boron nitride nanotubes, reducing the preparation cost of the boron nitride nanotubes and being beneficial to the wide application and industrial production of the boron nitride nanotubes.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing boron nitride nanotubes according to the present application;
FIG. 2 is an XRD diffraction pattern of effect example 1 of the present application;
FIG. 3 is a photograph of boron nitride nanotubes prepared in example 3 of the present application;
FIG. 4 is an analysis chart of effect example 2 of the present application;
FIG. 5 is a transmission electron microscope image of boron nitride nanotubes prepared in example 3 of the present application;
Fig. 6 is a scanning electron microscope image of effect example 3 of the present application.
Detailed Description
The present application will be described in detail below with reference to the embodiments shown in the drawings. The embodiments are not intended to limit the application, but structural, methodological, or functional modifications of the application from those skilled in the art are included within the scope of the application.
Boron Nitride Nanotubes (BNNTs) are one-dimensional hollow tubular nanomaterials composed of B and N through alternating covalent bonds that have been of great interest due to their unique physicochemical properties. BNNTs has similar mechanical strength and light weight characteristics as compared to carbon nanotubes, but has better high temperature and oxidation resistance than carbon nanotubes. Because of the polar bonding between B and N, BNNTs has strong interfacial bonding force with the polymer, and can be effectively used as a mechanical reinforcing phase of a high polymer material. Furthermore, electrical insulation (band gap of 5.5 eV) and neutron absorption are also important properties of BNNTs. Therefore, BNNTs has wide application prospect in the fields of thermal interface materials, high-temperature resistant materials, radiation shielding materials, deep ultraviolet emitters and the like. However, the market price of BNNTs is very expensive, which greatly limits its application. Therefore, how to prepare BNNTs at low cost is the focus of current research.
The preparation method of the boron nitride nanotube mainly comprises an ultrahigh temperature preparation technology and a high temperature preparation technology. The temperature of the ultra-high temperature preparation technology is generally above 2000 ℃, and the ultra-high temperature preparation technology mainly comprises laser ablation, thermal plasma and arc discharge methods, and the three methods can produce BNNTs with high quality, but the growth temperature is extremely high, so that the production cost is extremely high, and the ultra-high temperature preparation technology is not suitable for industrial mass production. The temperature of the high temperature preparation technique is generally 1100-1500 ℃, wherein the Chemical Vapor Deposition (CVD) method is simple in equipment and easy to control, and the obtained BNNTs is high in quality and is the most favored method.
In the current method for preparing BNNTs by CVD, the precursor is the most classical boron and metal oxide, or boron and metal compound, or boride and nitride, and the synthesis temperature of BNNTs is above 1100 ℃ because of the higher melting point, so that the application of CVD preparation BNNTs in industrial production is greatly limited.
In order to solve the problems, the applicant has developed a preparation method of a boron nitride nanotube, which can prepare a high quality boron nitride nanotube at a low growth temperature by preparing a precursor with a low melting point, thereby effectively reducing the production cost of the boron nitride nanotube and helping to improve the application scenario of the boron nitride nanotube.
Specifically, referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing boron nitride nanotubes according to the present application.
The preparation method comprises the following steps:
s100, weighing raw materials into a reactor, wherein the raw materials comprise carbonate, magnesium oxide and boron precursors.
And S200, heating the reactor to a reaction temperature in an inert atmosphere to generate a precursor.
Wherein the reaction temperature is 850-1200 ℃. Preferably, the reaction temperature may be 950-1200 ℃.
Firstly, carbonate, magnesium oxide and boron precursors can be used as raw materials, and in the process of heating to the reaction temperature, the carbonate, magnesium oxide and boron precursors can react to generate a precursor with low melting point.
In one embodiment, the molar ratio of carbonate, magnesium oxide and boron precursor in the feedstock may be 1:1 (2-6).
Preferably, the molar ratio of carbonate, magnesium oxide and boron precursor may be 1:1:4.
Specifically, in one embodiment, the boron precursor may be boron powder, and in other embodiments, the boron precursor may be another material containing boron element, such as sodium tetraborate, etc., which can achieve the effects of this embodiment.
In one embodiment, the carbonate may be potassium carbonate, and during the warming process, the potassium carbonate, magnesium oxide, and boron precursor may react to form KMgBO 3 precursor that contains both the boron source and the catalyst metal, and has a lower melting point, based on which the boron nitride precursor can be prepared at a lower temperature.
In another embodiment, the carbonate may also be sodium carbonate, and during the heating process, the sodium carbonate, magnesium oxide and boron precursor may react to form NaMgBO 3 precursor, which has a lower melting point, or may be prepared at a lower temperature.
In other embodiments, the carbonate may be other metal salts, and a low-melting-point precursor including both the boron source and the catalyst metal may be prepared and synthesized, thereby achieving the effects of this embodiment.
In one embodiment, the reactor may employ a boron nitride boat, and the reactor may be placed in a central heating location of a tube furnace through which the reactor is warmed to reaction temperature.
In other embodiments, other types of reactors, such as ceramic reactors, crucibles, etc., may be used, and other heating devices may be used, and the effect of this embodiment may be achieved by being able to raise the reaction temperature to 850 to 1200.
In one embodiment, in order to ensure stable reaction of the carbonate, magnesium oxide and boron precursors, the temperature may be raised specifically by raising the temperature of the reactor at a constant speed of 10-30 ℃ per minute. Preferably, the reactor may be warmed up at a constant rate of 20 ℃ per minute.
In one embodiment, the inert atmosphere may be argon gas with a flow rate of 20 to 100 standard cubic centimeters per minute, and in other embodiments, other types of inert gases may be used, such as nitrogen, helium, and the like.
And S300, placing the reactor in an ammonia gas atmosphere, maintaining the reaction temperature, and continuously reacting to generate the boron nitride nanotube.
After the low-melting-point precursor is generated on the reactor, ammonia gas can be used for replacing inert gas, so that the reactor is placed in an ammonia gas atmosphere, and the precursor continuously reacts with the ammonia gas at the reaction temperature to generate the boron nitride nanotube.
In one embodiment, the ammonia gas atmosphere may specifically be ammonia gas with a flow rate of 20-100 standard cubic centimeters per minute.
In one embodiment, the continuous reaction may be specifically a reaction for 60 to 180 minutes. Preferably, the continuous reaction may be specifically a reaction for 120min.
And S400, cooling the reactor to room temperature in an inert atmosphere to obtain the boron nitride nanotube.
Specifically, the inert atmosphere may be the same as that in step S200, or may be other inert gases, so that the boron nitride nanotubes at high temperature may be sufficiently protected.
It can be appreciated that by adopting the preparation method, the low-melting-point precursor is prepared by using the carbonate, the magnesium oxide and the boron precursor in the heating process, and then the boron nitride nanotube is generated by continuous reaction at a lower temperature, so that the growth temperature can be effectively reduced, the preparation cost of the boron nitride nanotube is reduced, and the wide application and industrial production of the boron nitride nanotube are facilitated.
The technical scheme of the application is further explained in detail in the following specific embodiments.
Example 1:
The preparation method of the boron nitride nanotube comprises the following steps:
Weighing potassium carbonate, magnesium oxide and boron powder according to a molar ratio of 1:1:4, placing the mixture in a boron nitride boat, and placing the boron nitride boat at the central heating position of a tube furnace. Argon with the temperature of 50 standard cubic centimeters per minute (sccm) is introduced into the tube furnace, the tube furnace is controlled to be heated to the central temperature of 850 ℃ at 20 ℃ per minute, and a KMgBO 3 precursor is generated by the reaction in the boron nitride boat in the heating process.
And then 50sccm ammonia gas is introduced into the tube furnace to replace argon gas, 850 ℃ is kept, and the reaction is continued for 120min to grow the boron nitride nanotube. And after the reaction is finished, introducing 50sccm argon into the tube furnace, and taking out after the sample is cooled to room temperature to obtain the boron nitride nanotube.
Example 2:
The preparation method of the boron nitride nanotube comprises the following steps:
Weighing potassium carbonate, magnesium oxide and boron powder according to a molar ratio of 1:1:2, placing the mixture in a boron nitride boat, and placing the boron nitride boat at the central heating position of a tube furnace. Argon of 20 standard cubic centimeters per minute (sccm) is introduced into the tube furnace, the tube furnace is controlled to be heated to the central temperature of 950 ℃ at 10 ℃ per minute, and a KMgBO 3 precursor is generated by the reaction in the boron nitride boat in the heating process.
And then 100sccm ammonia gas is introduced into the tube furnace to replace argon gas, the temperature is kept at 950 ℃, and the reaction is continued for 60 minutes to grow the boron nitride nanotube. And after the reaction is finished, introducing 20sccm argon into the tube furnace, and taking out after the sample is cooled to room temperature to obtain the boron nitride nanotube.
Example 3:
The preparation method of the boron nitride nanotube comprises the following steps:
Weighing sodium carbonate, magnesium oxide and boron powder according to a molar ratio of 1:1:6, placing the mixture in a boron nitride boat, and placing the boron nitride boat at the central heating position of a tube furnace. Argon with the temperature of 100 standard cubic centimeters per minute (sccm) is introduced into the tube furnace, the tube furnace is controlled to be heated to the central temperature of 1000 ℃ at 30 ℃ per minute, and a NaMgBO 3 precursor is generated by the reaction in the boron nitride boat in the heating process.
Then, 20sccm ammonia gas is introduced into the tube furnace to replace argon gas, the temperature is kept at 1000 ℃, and the reaction is continued for 180 minutes to grow the boron nitride nanotube. And after the reaction is finished, introducing 20sccm argon into the tube furnace, and taking out after the sample is cooled to room temperature to obtain the boron nitride nanotube.
Example 4:
The preparation method of the boron nitride nanotube comprises the following steps:
Weighing potassium carbonate, magnesium oxide and boron powder according to a molar ratio of 1:1:4, placing the mixture in a boron nitride boat, and placing the boron nitride boat at the central heating position of a tube furnace. Argon with the temperature of 50 standard cubic centimeters per minute (sccm) is introduced into the tube furnace, the tube furnace is controlled to be heated to the central temperature of 1100 ℃ at 20 ℃ per minute, and a KMgBO 3 precursor is generated by the reaction in the boron nitride boat in the heating process.
And then 50sccm ammonia gas is introduced into the tube furnace to replace argon gas, the temperature is kept at 1100 ℃, and the reaction is continued for 120min to grow the boron nitride nanotube. And after the reaction is finished, introducing 50sccm argon into the tube furnace, and taking out after the sample is cooled to room temperature to obtain the boron nitride nanotube.
Example 5:
The preparation method of the boron nitride nanotube comprises the following steps:
Weighing potassium carbonate, magnesium oxide and boron powder according to a molar ratio of 1:1:4, placing the mixture in a boron nitride boat, and placing the boron nitride boat at the central heating position of a tube furnace. Argon with the temperature of 50 standard cubic centimeters per minute (sccm) is introduced into the tube furnace, the tube furnace is controlled to be heated to the central temperature of 1200 ℃ at 20 ℃ per minute, and a KMgBO 3 precursor is generated by the reaction in the boron nitride boat in the heating process.
And then 50sccm ammonia gas is introduced into the tube furnace to replace argon gas, the temperature is kept at 1200 ℃, and the reaction is continued for 120min to grow the boron nitride nanotube. And after the reaction is finished, introducing 50sccm argon into the tube furnace, and taking out after the sample is cooled to room temperature to obtain the boron nitride nanotube.
Effect example 1:
XRD diffraction analysis is carried out on the precursor prepared in the embodiment 2, and a control experiment 1 and a control experiment 2 are designed, wherein the control experiment 1 takes magnesium oxide and boron powder with the molar ratio of 1:2 as raw materials, the precursor is prepared by the same steps as in the embodiment 2, the control experiment 2 takes potassium carbonate and boron powder with the molar ratio of 1:2 as raw materials, the precursor is prepared by the same steps as in the embodiment 2, and XRD diffraction analysis is carried out on the precursor of the control experiment 1 and the precursor of the control experiment 2, so that the figure 2 is obtained.
Referring to fig. 2, fig. 2 is an XRD diffractogram of effect example 1 of the present application, wherein a, b, c are the XRD diffractograms of the precursor prepared in control experiment 1, control experiment 2, and example 2, respectively.
As shown in FIG. a, the peak of the index 4 corresponds to Mg 2B2O5, the reaction of magnesium oxide and boron produces Mg 2B2O5 (JCCPDSCardNTO.73-2232) with a melting point of about 1400 ℃, as shown in FIG. b, the peak of the index 5 corresponds to K 2B4O7 (JCCPDSCardNO.70-1494), the reaction of potassium carbonate and boron powder produces potassium borate with a melting point of about 780 ℃, as shown in FIG. C, the peak of the index 6 corresponds to KMgBO 3 (. JCCPDS CardNO.174336), and the peak of the index 7 corresponds to Mg 3(BO3)2 (JCCPDSCardNO.33-0858).
From the above experiments, it was confirmed that the main product of the reaction of potassium carbonate, magnesium oxide and boron is magnesium potassium borate, which has a melting point between that of magnesium borate and potassium borate.
Effect example 2:
referring to fig. 3, fig. 3 is a photograph showing a boron nitride nanotube prepared in example 3 of the present application. As shown in the figure, as white powder.
XRD diffraction analysis, raman spectrum analysis and infrared spectrum analysis were performed on the boron nitride nanotubes prepared in example 3, respectively, to obtain FIG. 4.
Referring to fig. 4, fig. 4 is an analysis chart of effect example 2 of the present application, in which a is an XRD diffraction chart, b is a raman spectrum, and c is a FTIR spectrum.
As shown in the figure, XRD diffraction patterns show that the characteristic signals of h-BN are the 5 peaks of the (002), (100), (101), (102) and (110) planes, and correspond to the characteristic signals of h-BN in JCPDS card (No. 73-2095), and the samples after growth are proved to be pure h-BN structures.
Raman spectra show a strong absorption band at 1368cm -1, which is related to the E2g in-plane vibrational mode of h-BN.
Further, FTIR spectra showed that three absorption regions were obtained near 1520cm -1、1365cm-1 and 806cm -1. The absorption peak at 806cm -1 is a B-N-B flexural vibration parallel to the c-axis and the absorption peak at 1365cm -1 is a B-N tensile vibration perpendicular to the c-axis, which are all characteristic of BN. Whereas the absorption peak at 1520cm -1 belongs to the vibration of the BN skeleton in the tangential direction of the nanotubes, only observed in bnnt of high purity, high crystallinity.
Thus, it was confirmed based on the above-mentioned spectra that example 3 prepared high purity boron nitride.
Transmission electron microscopy analysis was performed on the prepared boron nitride nanotubes of example 3 to obtain fig. 5, and fig. 5 is a transmission electron microscopy image of the boron nitride nanotubes prepared in example 3 of the present application.
As shown in the figure, the prepared boron nitride nanotube has a hollow tubular structure.
Based on the above analysis, example 3 prepared high purity boron nitride nanotubes.
Effect example 3 characterization analysis
Scanning electron microscope analysis was performed on the boron nitride nanotubes prepared in examples 1 to 5, resulting in fig. 6.
Referring to fig. 6, fig. 6 is a scanning electron microscope image of effect example 3 of the present application, and a, b, c, d, e is an SEM image of the boron nitride nanotubes prepared in examples 1,2, 3, 4, and 5, respectively.
As shown, some boron nitride nanotubes have grown under the 850 ℃ reaction in example 1, but in smaller numbers. A large amount of high quality boron nitride nanotubes could be grown already in the 950 ℃ reaction in example 2, and a large amount of high quality boron nitride nanotubes could be grown in each of examples 3 to 5.
Thus, it can be seen from the above that the present application can grow boron nitride nanotubes at a relatively low temperature of 850 ℃ and obtain a large amount of high quality boron nitride nanotubes at 950 ℃.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310208969.7A CN116199194B (en) | 2023-03-07 | 2023-03-07 | Preparation method of boron nitride nanotubes and boron nitride nanotubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310208969.7A CN116199194B (en) | 2023-03-07 | 2023-03-07 | Preparation method of boron nitride nanotubes and boron nitride nanotubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116199194A CN116199194A (en) | 2023-06-02 |
| CN116199194B true CN116199194B (en) | 2025-01-03 |
Family
ID=86507486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310208969.7A Active CN116199194B (en) | 2023-03-07 | 2023-03-07 | Preparation method of boron nitride nanotubes and boron nitride nanotubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116199194B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103383A (en) * | 2014-01-06 | 2016-11-09 | 莫门蒂夫性能材料股份有限公司 | High length-diameter ratio boron nitride, method and the compositions containing described high length-diameter ratio boron nitride |
| CN107161961A (en) * | 2017-06-30 | 2017-09-15 | 武汉理工大学 | A kind of sea urchin shape boron nitride nanosheet nanotube hierarchy and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520714A (en) * | 2020-03-20 | 2021-03-19 | 山东晶亿新材料有限公司 | Hexagonal boron nitride and preparation method and application thereof |
| CN113353899B (en) * | 2021-05-24 | 2022-09-23 | 南京大学 | A kind of preparation method of boron nitride nanotube, boron nitride nanotube and application thereof |
| CN113213438A (en) * | 2021-06-23 | 2021-08-06 | 南京大学 | Boron nitride nanotubes and method for producing the same |
-
2023
- 2023-03-07 CN CN202310208969.7A patent/CN116199194B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103383A (en) * | 2014-01-06 | 2016-11-09 | 莫门蒂夫性能材料股份有限公司 | High length-diameter ratio boron nitride, method and the compositions containing described high length-diameter ratio boron nitride |
| CN107161961A (en) * | 2017-06-30 | 2017-09-15 | 武汉理工大学 | A kind of sea urchin shape boron nitride nanosheet nanotube hierarchy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116199194A (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Synthesis of high crystalline beta SiC nanowires on a large scale without catalyst | |
| US20060051281A1 (en) | Metal carbides and process for producing same | |
| JP2010180066A (en) | Boron nitride spherical nanoparticle and method of producing the same | |
| Li et al. | Synthesis of zirconium carbide whiskers by a combination of microwave hydrothermal and carbothermal reduction | |
| JP2019524612A (en) | Boron nitride nanomaterial, its production method and application | |
| Tong et al. | Thermal plasma synthesis of SiC nano-powders/nano-fibers | |
| JP5059589B2 (en) | Boron nitride nanofiber and method for producing the same | |
| Merenkov et al. | Extraordinary synergetic effect of precursors in laser CVD deposition of SiBCN films | |
| Liu et al. | Effect of SiC content on microstructure evolution of ZrB2-ZrC-SiC ceramic in sol-gel process | |
| WO2003010114A1 (en) | A method of producing nanometer silicon carbide material | |
| JP4817103B2 (en) | Method for producing boron nitride nanotubes | |
| JP2004161546A (en) | Method of forming boron nitride precursor and method of manufacturing boron nitride nanotube using boron nitride precursor | |
| CN107161960B (en) | A kind of high pressure vapor prepares the method and apparatus of boron nitride spherical powder | |
| CN116199194B (en) | Preparation method of boron nitride nanotubes and boron nitride nanotubes | |
| Sun et al. | Synthesis of SiC/SiO2 nanochains by carbonthermal reduction process and its optimization | |
| CN111268656A (en) | Preparation method of boron nitride nanotube | |
| CN116986906A (en) | Two-dimensional transition metal compound, preparation method and application thereof based on MXene | |
| CN112794330B (en) | A kind of preparation method of boron carbide nanowires | |
| CN113353899A (en) | Preparation method of boron nitride nanotube, boron nitride nanotube and application of boron nitride nanotube | |
| JP3882077B2 (en) | Method for producing boron nitride nanotubes using gallium oxide as a catalyst | |
| CN110685012B (en) | Porous ferronitrogen single crystal material and preparation method and application thereof | |
| CN117105185A (en) | Carrier auxiliary preparation method of boron nitride nanotube and boron nitride nanotube | |
| JP3893465B2 (en) | Method for producing boron nitride nanotubes | |
| CN1292986C (en) | Process for preparing silicon carbide nano fibre | |
| JP3658622B2 (en) | Method for producing boron carbide nanowire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |