CN114524418A - Preparation method of mallet-shaped short boron nitride nanotube - Google Patents
Preparation method of mallet-shaped short boron nitride nanotube Download PDFInfo
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Abstract
The invention discloses a preparation method of a mallet-shaped short boron nitride nanotube, which comprises the following steps: firstly, mixing boron oxide and metal magnesium powder and performing ball milling to obtain solid powder; secondly, putting the solid powder into a porcelain boat, putting a low-iron-content nichrome wire mesh on the porcelain boat, heating to 1250-1350 ℃ under the protection of argon, introducing high-purity ammonia gas for heat preservation, and depositing to obtain the mallet-shaped short boron nitride nanotube. The invention catalyzes the boron oxide and magnesium powder to generate B at high temperature after ball milling and activation2O2Gas diffuses to the nickel-chromium alloy wire mesh to react with ammonia gas to generate BN nano-tubes, the growth speed of the catalytic generation of the BN nano-tubes is controlled by the low iron content of the nickel-chromium alloy wire mesh, a gas-liquid-solid growth mechanism is combined to ensure that the rod-shaped short boron nitride nano-tubes are obtained, the product is easy to disperse uniformly as an additive, the performance of a composite material matrix is effectively improved, and the boron nitride nano-tube is suitable for high-performance structural materials and functional material collars for equipment and machineryA domain.
Description
Technical Field
The invention belongs to the technical field of synthesis of hexagonal boron nitride micro-nano materials, and particularly relates to a preparation method of a mallet-shaped short boron nitride nanotube.
Background
Boron nitride has the molecular formula BN, and is a graphite-like layered structure material composed of nitrogen (N) atoms and boron (B) atoms. The BN nano material refers to a BN material with at least one dimension in a nano scale range in a three-dimensional space. Due to the small size effect, the BN nano material has the advantages of high specific surface area, good adsorptivity and the like on the basis of good mechanical property, higher thermal conductivity, obvious electrical insulation, excellent chemical stability and excellent oxidation resistance of the bulk BN material. The unique properties enable the BN nano material to have good application prospects in the fields of biological probes, photoelectric instruments, humidity sensing, hydrogen storage media and the like, and particularly show the advantages in high-temperature and corrosive environments.
The research on the BN nano-material relates to BN nano-materials with various morphologies such as nanotubes, nanowires, nanosheets, nanospheres and the like, wherein the BN nanotube of the contemporary genus, which is researched earliest, at most, is mature. The BN nanotubes reported in the literature at present have bamboo joint type, cylindrical type, corrugated type and the like. The length is generally long, about more than ten microns. Short BN nanotubes with the length of less than 5 mu m are not reported, and BN nanotubes shaped like a club are not reported. The application fields will be different due to the differences in properties of BN nanotubes of different sizes and morphologies. Therefore, it is very necessary to prepare boron nitride nanotubes with different lengths and morphologies.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a mallet-shaped short boron nitride nanotube in view of the above-mentioned deficiencies of the prior art. In the method, boron oxide and magnesium powder are subjected to ball milling activation to generate B in the annealing process2O2The gas diffuses to the nickel-chromium alloy wire mesh and reacts with ammonia gas to generate BN nano-tubes, the growth speed of the catalytic generation of the BN nano-tubes is controlled by the low iron content of the nickel-chromium alloy wire mesh, and the gas-liquid-solid growth mechanism of the BN nano-tubes, which is generated by the reaction after B atoms and N atoms are absorbed into nickel-chromium alloy small drops and saturated, is combined, so that the short length and the shape of the BN nano-tubes are effectively ensuredForming a mallet-shaped structure to obtain the mallet-shaped short boron nitride nanotube.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a mallet-shaped short boron nitride nanotube is characterized by comprising the following steps:
mixing boron oxide and metal magnesium powder according to a molar ratio of 1: 1.5-1: 2.5, and then ball-milling for 2-12 h in a protective atmosphere by using a planetary ball mill to obtain solid powder with the particle size of 2-10 mu m;
and step two, placing the solid powder obtained in the step one in a porcelain boat, placing a low-iron-content nichrome wire mesh at the central position of the upper part of the porcelain boat, heating the porcelain boat from room temperature to 1250-1350 ℃ at the speed of 10 ℃/min under the protection of argon, closing an argon valve, introducing high-purity ammonia gas, preserving the heat for 2-8 h, stopping introducing the high-purity ammonia gas, naturally cooling the porcelain boat to room temperature under a protective atmosphere, and depositing an off-white substance on the nichrome wire mesh to obtain the rod-shaped short boron nitride nanotube.
According to the method, boron oxide and metal magnesium powder are mixed and ball-milled to obtain solid powder, the molar ratio of the raw material boron oxide to the catalyst metal magnesium powder is controlled, the forming process and the production amount of the BN nano tube are effectively adjusted, the morphology of the BN nano tube is further controlled, and the preparation of the hammer-shaped short boron nitride nano tube is facilitated; then placing the solid powder in a porcelain boat, placing a nickel-chromium alloy wire mesh with low iron content on the upper part of the porcelain boat, firstly introducing argon to remove air, heating to 1250-1350 ℃, then introducing high-purity ammonia gas, carrying out heat preservation annealing, in the process, ball-milling, mixing and activating magnesium powder serving as a catalyst and boron oxide serving as a raw material, and generating B at high temperature2O2And gas is diffused to the low-iron-content nickel-chromium alloy wire mesh, and the BN nano tube is formed on the low-iron-content nickel-chromium alloy wire mesh through vapor deposition and slowly grows under the slow catalytic action of iron and the synergistic combined catalytic action of nickel and chromium, so that the short boron nitride nano tube with short length is obtained. The invention adopts the nichrome wire mesh with low iron content to form lower catalytic speed, so that the BN nano tube grows slowly, and the short BN nano tube is preparedThe boron nitride nanotube avoids the defects that the BN nanotube grows too fast due to the excessively strong catalytic performance of the high-iron-content nickel-chromium alloy wire mesh, and the prepared boron nitride nanotube is longer, and the low-iron-content nickel-chromium alloy wire mesh is usually placed in the central position of the upper part of a porcelain boat so as to facilitate the circulation of reaction gas; meanwhile, a small nickel-chromium alloy liquid drop is formed on the surface layer of the nickel-chromium alloy wire mesh at high temperature and is diffused to B on the nickel-chromium alloy wire mesh2O2B atoms in gas and N atoms in reaction gas ammonia are absorbed and dissolved in a nickel-chromium alloy small drop, BN generated by reaction is separated from the small drop and forms a capsule-shaped BN along with the increase of the concentration of the B atoms and the concentration of the N atoms and the gradual saturation state, the capsule-shaped BN is a section of a bamboo joint type nano tube, the diameter of the capsule-shaped BN is larger, a plurality of bamboo joints are connected together along with the extension of reaction time to form the bamboo joint type BN nano tube, meanwhile, the formed bamboo joint type BN nano tube is gradually elongated and becomes thin under the action of internal stress, and as the action time of the internal stress is longest, the diameter of the first section of the bamboo joint type nano tube is smallest, the action time of the internal stress of the last section is shortest, and the diameter of the formed bamboo joint type BN is largest, so that the mallet-shaped short nano tube with one thick end and one thin end is formed.
The preparation method of the rod-shaped short boron nitride nanotube is characterized in that the protective atmosphere in the first step and the second step is nitrogen, helium, neon, argon, krypton, xenon or radon.
The preparation method of the hammer-shaped short boron nitride nanotube is characterized in that in the second step, the flow of argon is 20 mL/min-100 mL/min, and the flow of high-purity ammonia gas is 50 mL/min-200 mL/min. The invention can quickly and fully evacuate the air in the reaction device by controlling the flow of the argon; through the flow of control high-purity ammonia, effective control reaction rate avoids the reaction rate that high-purity ammonia lets in the too big reaction rate that leads to of volume too fast for the diameter of the BN nanotube that the reaction generated is thick, can't obtain the short boron nitride nanotube of stick hammer.
The preparation method of the rod-shaped short boron nitride nanotube is characterized in that in the second step, the low-iron-content nichrome wire mesh is replaced by a low-iron-content metal wire mesh and a metal porous material, a metal and ceramic solid sheet, a ceramic wire mesh and a ceramic porous material.
The preparation method of the hammer-shaped short boron nitride nanotube is characterized in that in the step one, the solid powder contains catalyst metal magnesium powder and iron powder generated by ball milling. In the process of mixing and ball-milling the boron oxide and the metal magnesium powder, a very small amount of iron powder is introduced under the action of friction and collision of grinding balls (usually stainless steel grinding balls), and the iron powder also has a catalytic action and is beneficial to catalyzing the boron oxide reaction to generate B2O2A gas.
The preparation method of the rod-shaped short boron nitride nanotube is characterized in that the iron content of the low-iron-content nichrome wire mesh in the second step is lower than 1 wt%. The nickel-chromium alloy wire mesh containing iron effectively controls the growth speed of the BN nano tube, and is beneficial to obtaining the hammer-shaped short boron nitride nano tube.
The preparation method of the hammer-shaped short boron nitride nanotube is characterized in that in the second step, the diameter of the thick end of the hammer-shaped short boron nitride nanotube is 100 nm-300 nm, the diameter of the thin end of the hammer-shaped short boron nitride nanotube is 20 nm-60 nm, and the length of the hammer-shaped short boron nitride nanotube is 2 mu m-3 mu m.
Compared with the prior art, the invention has the following advantages:
1. the invention carries out ball milling activation on raw material boron oxide and catalyst magnesium powder, and then carries out catalysis at high temperature to generate B2O2The gas diffuses to the nickel-chromium alloy wire mesh, and the ammonia gas and the B are catalyzed by iron, nickel and chromium in the nickel-chromium alloy wire mesh2O2The BN nano tube is generated through gas reaction, the growth speed of the BN nano tube generated through catalysis is controlled through the low iron content of the nickel-chromium alloy wire mesh, and the short length of the BN nano tube is effectively ensured and a mallet-shaped structure is formed by combining a gas-liquid-solid growth mechanism formed by reaction and precipitation after B atoms and N atoms are absorbed into nickel-chromium alloy small drops to be saturated, so that the mallet-shaped short boron nitride nano tube is obtained.
2. The club-shaped short boron nitride nanotube prepared by the invention has the advantages of the diameter of the thick end of 100 nm-300 nm, the diameter of the thin end of 20 nm-60 nm, the length of 2 mu m-3 mu m and short length, is not easy to wind and agglomerate when being used as a composite material additive, is easy to disperse uniformly, and plays a role in improving the mechanical property, the heat transfer property, the high temperature resistance, the corrosion resistance and the like of a base material.
3. The prepared short boron nitride nanotube with a mallet shape is used as a composite material additive, effectively improves the mechanical property, the heat transfer property, the high temperature resistance and the corrosion resistance of a composite material matrix, and is suitable for the fields of high-performance structural materials and functional materials for equipment and machinery.
4. The raw materials of the preparation method of the invention, namely the boron oxide powder, the metal magnesium powder, the nickel-chromium alloy wire mesh, the argon gas and the high-purity ammonia gas, belong to common chemical raw materials which are already industrially produced, and have the advantages of wide sources, low price, easy obtainment, no toxicity and no harm.
5. The invention prepares the reaction precursor through the ball milling activation process, and then the final product can be prepared through heating of a conventional tubular atmosphere protective annealing furnace, the requirement on preparation equipment is not high, and the ball milling activation reduces the reaction temperature, thereby reducing the energy consumption and the production cost of the whole preparation process.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is an XRD pattern of a short boron nitride nanotube formed in a shape of a mallet prepared in example 1 of the present invention.
FIG. 2a is an SEM image of a short boron nitride nanotube with a mallet shape prepared in example 1 of the present invention.
FIG. 2b is the EDS energy spectrum of the surface of the NiCr alloy wire mesh on which the Tacroma-like short boron nitride nanotubes are deposited in example 1 of the present invention.
FIG. 3 is a TEM image of the short boron nitride nanotubes prepared in example 1 of the present invention.
FIG. 4 is a diffraction pattern of selected areas of the short boron nitride nanotubes prepared in example 1 of the present invention.
FIG. 5 is a high resolution TEM image of single-rod hammer-shaped short BN nanotubes prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, mixing boron oxide and metal magnesium powder according to a molar ratio of 1:2, placing the mixture in a planetary ball mill, and then performing ball milling for 4 hours in a protective atmosphere nitrogen by adopting a positive and negative rotation alternate operation mode to obtain solid powder with the particle size of 2-10 microns;
and step two, placing the solid powder obtained in the step one in a porcelain boat, placing a 30mm multiplied by 30mm (length multiplied by width) nichrome wire mesh with the iron content of 0.7 wt% at the central position of the upper part of the porcelain boat, then closing an argon valve when the temperature is raised from room temperature to 1300 ℃ at the speed of 10 ℃/min under the protection of argon with the flow rate of 20mL/min, introducing ammonia with the mass purity of 99.99% at the flow rate of 150mL/min, preserving the heat for 6h, stopping introducing the ammonia, naturally cooling to the room temperature under the protection atmosphere of argon, and depositing an off-white substance on the nichrome wire mesh to obtain the rod-shaped short boron nitride nanotube.
In the first step of this embodiment, the protective atmosphere nitrogen may be replaced by helium, neon, argon, krypton, xenon, or radon; the protective atmosphere argon in the second step can be replaced by nitrogen, helium, neon, krypton, xenon or radon; the flow rate of the argon gas introduced in advance in the second step can be a value within 20 mL/min-100 mL/min except 20 mL/min.
Fig. 1 is an XRD pattern of the short boron nitride nanotube prepared in this example, and it can be seen from fig. 1 that there is a sharp and clear BN phase diffraction peak in the XRD pattern of the short boron nitride nanotube, which indicates that the product of this example is boron nitride and has good crystallization, and at the same time, there are strong nickel peak and chromium peak because the short boron nitride nanotube grows on the nichrome wire mesh.
Fig. 2a is an SEM image of the short boron nitride nanotube in the shape of a mallet prepared in this example, and it can be seen from fig. 2a that the short boron nitride nanotube in the shape of a mallet is prepared uniformly and densely on the surface of the nichrome wire mesh in this example, and the nanotube is thick at one end and thin at the other end, is similar to a mallet, and has uniform length and diameter size, length of about 2 μm to 3 μm, diameter of the thick end of about 100nm to 300nm, and diameter of the thin end of about 20nm to 60 nm.
Fig. 2B is an EDS energy spectrum of the surface of the nichrome mesh on which the mallet-shaped short boron nitride nanotubes are deposited in this embodiment, and as can be seen from fig. 2B, the nichrome mesh mainly contains elements such as B, N, O, Al, Mg, Cr, Ni, and the like, where Al is caused by a porcelain boat, O is derived from magnesium oxide, Mg is derived from magnesium oxide, Cr, Ni are derived from the mesh, and the remaining elements are B and N, and the atomic ratio thereof is approximately 1:1, which meets the chemical equivalent characteristics of a BN material, and illustrates that the rod-shaped structure deposited on the surface of the nichrome mesh by the method of this embodiment is BN.
Fig. 3 is a TEM image of the mallet-shaped short boron nitride nanotube prepared in this example, and it can be seen from fig. 3 that the mallet-shaped short boron nitride nanotube is a bamboo-joint-type hollow tubular structure, one end of which is thick and the other end of which is thin, the diameter of the thick end is about 200nm, the diameter of the thin end is about 50nm, and both the thick end and the thin end are closed structures.
Fig. 4 is a diffraction diagram of a selected area of the hammer-shaped short boron nitride nanotube prepared in this embodiment, and it can be seen from fig. 4 that the product component of this embodiment is hexagonal boron nitride.
Fig. 5 is a high-resolution transmission electron micrograph of the single-mallet short boron nitride nanotube prepared in this example, and it can be seen from fig. 5 that the interplanar spacing of the single-mallet short boron nitride nanotube is about 0.334nm, which is in accordance with the interplanar spacing of hexagonal boron nitride, further indicating that the nanotube is a well-crystallized boron nitride nanotube.
As can be seen from fig. 1 to 5, the product prepared by the method of this example is a hexagonal boron nitride nanotube with good crystallization.
Example 2
The present embodiment is different from embodiment 1 in that: and in the second step, the temperature is increased to 1250 ℃.
Example 3
The present embodiment is different from embodiment 1 in that: in the second step, the temperature is raised to 1350 ℃.
Example 4
The present embodiment is different from embodiment 1 in that: in the first step, the molar ratio of the boron oxide to the metal magnesium powder is 1: 1.5.
Example 5
The present embodiment is different from embodiment 1 in that: in the first step, the molar ratio of the boron oxide to the metal magnesium powder is 1: 2.5.
Example 6
The present embodiment is different from embodiment 1 in that: the ball milling time in the step one is 2 hours.
Example 7
The present embodiment is different from embodiment 1 in that: the ball milling time in the step one is 6 h.
Example 8
The present embodiment is different from embodiment 1 in that: the ball milling time in the step one is 8 h.
Example 9
The present embodiment is different from embodiment 1 in that: the ball milling time in the step one is 10 hours.
Example 10
The present embodiment is different from embodiment 1 in that: the ball milling time in the first step is 12 h.
Example 11
The present embodiment is different from embodiment 1 in that: and the heat preservation time in the second step is 2 hours.
Example 12
The present embodiment is different from embodiment 1 in that: and in the second step, the heat preservation time is 4 h.
Example 13
The present embodiment is different from embodiment 1 in that: and the heat preservation time in the second step is 8 hours.
Example 14
The present embodiment is different from embodiment 1 in that: and the flow rate of the high-purity ammonia gas in the step two is 50 mL/min.
Example 15
The present embodiment is different from embodiment 1 in that: and the flow rate of the high-purity ammonia gas in the step two is 200 mL/min.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. A preparation method of a mallet-shaped short boron nitride nanotube is characterized by comprising the following steps:
mixing boron oxide and metal magnesium powder according to a molar ratio of 1: 1.5-1: 2.5, and then ball-milling for 2-12 h in a protective atmosphere by using a planetary ball mill to obtain solid powder with the particle size of 2-10 mu m;
and step two, placing the solid powder obtained in the step one in a porcelain boat, placing a low-iron-content nichrome wire mesh at the central position of the upper part of the porcelain boat, heating the porcelain boat from room temperature to 1250-1350 ℃ at the speed of 10 ℃/min under the protection of argon, closing an argon valve, introducing high-purity ammonia gas, preserving the heat for 2-8 h, stopping introducing the high-purity ammonia gas, naturally cooling the porcelain boat to room temperature under a protective atmosphere, and depositing an off-white substance on the nichrome wire mesh to obtain the rod-shaped short boron nitride nanotube.
2. The method as claimed in claim 1, wherein the protective atmosphere in the first and second steps is nitrogen, helium, neon, argon, krypton, xenon, or radon.
3. The method of claim 1, wherein the flow rate of argon gas in step two is 20-100 mL/min, and the flow rate of high purity ammonia gas is 50-200 mL/min.
4. The method as claimed in claim 1, wherein in step two the low-iron content nichrome mesh is replaced by a low-iron content metal mesh and porous metal material, a solid metal and ceramic sheet, a ceramic mesh and porous ceramic material.
5. The method of claim 1, wherein the solid powder in step one comprises magnesium powder as a catalyst and iron powder produced by ball milling.
6. The method of claim 1, wherein in step two the low iron content nichrome mesh contains less than 1 wt% iron.
7. The method as claimed in claim 1, wherein the diameter of the thick end of the short boron nitride nanotube is 100 nm-300 nm, the diameter of the thin end is 20 nm-60 nm, and the length is 2 μm-3 μm.
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| DE1667583A1 (en) * | 1966-03-09 | 1970-07-02 | Lonza Werk Gmbh | Process for the production of hexagonal boron nitride |
| GB1516689A (en) * | 1974-12-30 | 1978-07-05 | Kempten Elektroschmelz Gmbh | Manufacture of boron nitride |
| JPS61215203A (en) * | 1985-03-21 | 1986-09-25 | Toshiba Tungaloy Co Ltd | Synthesis of cubic boron nitride |
| CN1899956A (en) * | 2006-06-27 | 2007-01-24 | 华南理工大学 | Method for synthesizing single shape boron nitride nano tube |
| CN108545708A (en) * | 2018-03-14 | 2018-09-18 | 中国人民解放***箭军工程大学 | A kind of preparation method of the micro-nano section of jurisdiction composite construction of coralliform hexagonal boron nitride |
| CN111569530A (en) * | 2020-05-26 | 2020-08-25 | 中国人民解放***箭军工程大学 | Super-hydrophobic filter screen and preparation method thereof |
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2022
- 2022-02-16 CN CN202210141952.XA patent/CN114524418B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1667583A1 (en) * | 1966-03-09 | 1970-07-02 | Lonza Werk Gmbh | Process for the production of hexagonal boron nitride |
| GB1516689A (en) * | 1974-12-30 | 1978-07-05 | Kempten Elektroschmelz Gmbh | Manufacture of boron nitride |
| JPS61215203A (en) * | 1985-03-21 | 1986-09-25 | Toshiba Tungaloy Co Ltd | Synthesis of cubic boron nitride |
| CN1899956A (en) * | 2006-06-27 | 2007-01-24 | 华南理工大学 | Method for synthesizing single shape boron nitride nano tube |
| CN108545708A (en) * | 2018-03-14 | 2018-09-18 | 中国人民解放***箭军工程大学 | A kind of preparation method of the micro-nano section of jurisdiction composite construction of coralliform hexagonal boron nitride |
| CN111569530A (en) * | 2020-05-26 | 2020-08-25 | 中国人民解放***箭军工程大学 | Super-hydrophobic filter screen and preparation method thereof |
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