CN111377449A - Preparation method of boron carbide nanoparticles - Google Patents
Preparation method of boron carbide nanoparticles Download PDFInfo
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- CN111377449A CN111377449A CN201811617858.7A CN201811617858A CN111377449A CN 111377449 A CN111377449 A CN 111377449A CN 201811617858 A CN201811617858 A CN 201811617858A CN 111377449 A CN111377449 A CN 111377449A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/991—Boron carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention relates to a preparation method of boron carbide nano particles, which uses boron powder as a raw material, a carbon material as a reducing agent and a transition metal inorganic salt as a catalyst to generate B by heating and reducing in a furnace4C, nano-particles; the boron powder and the carbon material are mixed according to the molar ratio of (1-20): 1, adding 1-60% of transition metal inorganic salt catalyst by mass; absolute ethyl alcohol is used as a solvent, the mixture is uniformly mixed by ultrasonic waves, and the mixture is dried and heated in a high-temperature furnace to prepare a product. The invention has the advantages that the chemical analysis result proves that the boron and the carbon completely react, the prepared boron carbide reaches the nanometer level, the size distribution is narrow, the appearance is uniform, and the purity is high. The prepared boron carbide particles can be used for sintering ceramic products, and the ceramic products have higher bulletproof effect and neutron absorption effect than the current micron-level boron carbide due to the nanometer effect.
Description
Technical Field
The invention relates to the technical field of metallurgical chemical industry, in particular to a preparation method of boron carbide nanoparticles.
Background
The boron carbide has the advantages of high melting point, high hardness, good wear resistance, acid and alkali corrosion resistance, low density and strong thermal neutron absorption capacity due to the property of covalent bonds. Boron carbide is used as the lightest ceramic material, can be used as a jet plane blade due to low density, and is widely applied in the field of aerospace; can be used as a control rod of a nuclear reactor and a material for preventing radioactive substances from leaking due to its high neutron absorption capacity. However, the high-performance boron carbide ceramic product depends on higher-quality powder, and the preparation of the superfine nano powder always troubles the further development of boron carbide. According to the different reaction principle, raw material and equipment adopted for synthesizing boron carbide powder, the industrial preparation method of boron carbide powder mainly includes carbon tube furnace, electric arc furnace carbothermic reduction method and high-temperature self-propagating synthesis method. The carbon tube furnace and the electric arc furnace carbon thermal reduction method have the defects of high energy consumption, low production capacity, serious damage to the furnace body at high temperature and large average particle size of synthesized original powder. The residues in the reactants from the high temperature self-propagating synthesis must be washed away by additional processes and are extremely difficult to remove completely. Therefore, it is very difficult to obtain nano-scale particles by the current technical means.
Disclosure of Invention
The invention aims to solve the problem of high difficulty in obtaining nano-scale boron carbide particles in the prior art, and provides a preparation method of the nano-scale boron carbide particles.
The specific scheme of the invention is as follows: a preparation method of nano boron carbide particles comprises the following steps:
s1: according to a molar ratio (1-10): 1, mixing boron powder and a carbon source according to a proportion to obtain a black mixture A;
s2: mixing a black mixture A, a transition metal inorganic salt and absolute ethyl alcohol according to a mass ratio of 100: (1-50): (100-1000) ultrasonically stirring to obtain black slurry;
s3: drying the obtained black slurry in an oven (30-300 ℃) for 0.2-12 hours to obtain a black dry mixture;
s4: placing the obtained black dry mixture in a graphite crucible, heating the mixture to 700-1600 ℃ by using a high-temperature furnace under the gas atmosphere, preserving the heat for 0.1-6 h, and cooling to obtain black boron carbide powder;
s5: placing the obtained black boron carbide powder in heating equipment at the temperature of 300-900 ℃ for heat preservation for 1-12 h, and removing free carbon powder; washing with acid solution to remove catalyst and B2O3Then, centrifugal operation is carried out to obtain centrifugal precipitate;
s6: and drying the obtained centrifugal precipitate for 0.2-12 h in an oven at the temperature of 30-200 ℃ to obtain boron carbide particles.
The invention adoptsBoron powder and carbon material are used as raw materials, and transition metal inorganic salt is added as a catalyst for reducing the required reaction temperature. By controlling the sintering process and raw materials, the nano boron carbide particles with narrow particle size distribution and uniform appearance can be obtained. The reaction equation is as follows: b + C = B4C。
Preferably, the carbon source in step S1 is one of flake graphite, microcrystalline graphite, acetylene black, activated carbon, graphene, carbon nanotubes, or hollow carbon spheres.
Preferably, the ultrasonic stirring time in the step S2 is 1-30 min.
Preferably, the cooling rate in step S4 is 1-20 ℃/min.
Preferably, the gas in step S4 is one of helium and argon.
Preferably, the gas in step S4 is one of air, oxygen and carbon dioxide.
Preferably, the acid solution in step S5 is one of sulfuric acid, hydrochloric acid, and nitric acid.
Compared with the existing preparation method of boron carbide particles, the preparation method has the following substantial effects: the operation is simple, the raw materials are mixed and dried, the requirement on equipment is low, and large-scale industrial production can be realized; the catalyst is added during preparation, the required temperature is low, the requirement on high-temperature furnace equipment is low, the energy is saved, and the cost is low; the obtained product has high purity and simple subsequent treatment; the obtained product has uniform effect appearance and narrow particle size distribution, and boron carbide nano particles with the particle size of 50-300nm can be obtained through process regulation.
Drawings
FIG. 1 is an X-ray diffraction photograph of a product obtained in an example of the present invention;
FIG. 2 is a scanning electron micrograph of a product obtained in accordance with an example of the present invention;
FIG. 3 is a TEM image of the product obtained in the example of the present invention.
The specific implementation mode is as follows:
the invention will be further described with reference to the accompanying drawings in which:
a preparation method of nano boron carbide particles comprises the following steps:
s1: according to a molar ratio (1-10): 1, mixing boron powder and a carbon source according to a proportion to obtain a black mixture A; the carbon source is one of crystalline flake graphite, microcrystalline graphite, acetylene black, activated carbon, graphene, carbon nano tubes or hollow carbon spheres, and the molar ratio of the boron powder to the carbon source is 4: 1.
s2: mixing a black mixture A, a transition metal inorganic salt and absolute ethyl alcohol according to a mass ratio of 100: (1-50): (100-1000) ultrasonically stirring to obtain black slurry; the ultrasonic stirring time is 10-20 min; wherein the mass fraction ratio of the transition metal inorganic salt to the black mixture A is 1-10%, and can be 5%.
S3: and (3) drying the obtained black slurry in an oven (30-300 ℃) for 0.2-12 hours to obtain a black dry mixture, wherein the oven temperature can be set to 70 ℃, and the drying time can be set to 3-5 hours.
S4: and (3) placing the obtained black dry mixture in a graphite crucible, heating to 700-1600 ℃ by using a high-temperature furnace under the gas atmosphere, preserving heat for 0.1-6 h, and cooling to obtain black boron carbide powder. Wherein, the gas of the gas atmosphere can be one of helium or argon; the heating control mode of the high-temperature furnace can be set as follows: the temperature is increased from room temperature to 500 ℃ within 100min, then the temperature is increased from 500 ℃ to 800 ℃ within 30min, then the temperature is increased from 800 ℃ to 1000 ℃ within 40min, finally the temperature is increased from 1000 ℃ to 1160 ℃ within 64min, and the temperature is cooled at the rate of 1-20 ℃/min after the temperature is kept for 4 h. S5: placing the obtained black boron carbide powder in heating equipment at the temperature of 300-900 ℃ for heat preservation for 1-12 h, and removing free carbon powder; washing with acid solution to remove catalyst and B2O3Then, centrifugal operation is carried out to obtain centrifugal precipitate; wherein; the acid solution can be 20% sulfuric acid, the heating equipment can be a muffle furnace, the heat preservation temperature is set to be 400-800 ℃, and the heat preservation time is set to be 4-8 hours.
S6: and drying the obtained centrifugal precipitate for 0.2-12 h in an oven at the temperature of 30-200 ℃ to obtain boron carbide particles. The temperature of the oven may be set to 80 ℃ and the drying time may be set to 12 h.
Example (b):
weighing 0.174 g of nickel nitrate hexahydrate in a 500ml beaker, adding absolute ethyl alcohol to dissolve the nickel nitrate, weighing 2.7g of amorphous boron powder and 0.81g of high-conductivity carbon spheres, adding the amorphous boron powder and the high-conductivity carbon spheres into the obtained solution, and placing the solution in ultrasonic equipment to perform ultrasonic stirring for 15min to obtain black slurry; drying the obtained black slurry in a 70 ℃ oven for 3 h, then placing the black slurry in a graphite crucible and placing the graphite crucible on a high-temperature furnace, increasing the temperature from room temperature to 500 ℃ within 100min, increasing the temperature from 500 ℃ to 800 ℃ within 30min, increasing the temperature from 800 ℃ to 1000 ℃ within 40min, finally increasing the temperature from 1000 ℃ to 1160 ℃ within 64min, introducing argon as protective gas, preserving the temperature for 4h, then placing the black slurry in a 800 ℃ muffle furnace, removing free carbon powder, and ultrasonically cleaning by using a 20% sulfuric acid solution to remove the catalyst and B2O3Centrifuging to obtain powder, and drying the powder in an oven at 80 ℃ for 12h to obtain a final product, namely the boron carbide particles.
The XRD pattern of the boron carbide particles obtained in the present embodiment is shown in fig. 1, from which only the diffraction peak of boron carbide can be clearly seen, and as shown in fig. 2 and 3, the diameter of the obtained boron carbide particles is 50 to 100nm, and reaches the nanometer level.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (7)
1. A preparation method of nano boron carbide particles is characterized by comprising the following steps:
s1: according to a molar ratio (1-10): 1, mixing boron powder and a carbon source according to a proportion to obtain a black mixture A;
s2: mixing a black mixture A, a transition metal inorganic salt and absolute ethyl alcohol according to a mass ratio of 100: (1-50): (100-1000) ultrasonically stirring to obtain black slurry;
s3: drying the obtained black slurry in an oven (30-300 ℃) for 0.2-12 hours to obtain a black dry mixture;
s4: placing the obtained black dry mixture in a graphite crucible, heating the mixture to 700-1600 ℃ by using a high-temperature furnace under the gas atmosphere, preserving the heat for 0.1-6 h, and cooling to obtain black boron carbide powder;
s5: placing the obtained black boron carbide powder in heating equipment at the temperature of 300-900 ℃ for heat preservation for 1-12 h, and removing free carbon powder; washing with acid solution to remove catalyst and B2O3Then, centrifugal operation is carried out to obtain centrifugal precipitate;
s6: and drying the obtained centrifugal precipitate for 0.2-12 h in an oven at the temperature of 30-200 ℃ to obtain boron carbide particles.
2. The method of claim 1, wherein the carbon source in step S1 is one of flake graphite, microcrystalline graphite, acetylene black, activated carbon, graphene, carbon nanotubes, or hollow carbon spheres.
3. The method for preparing nano boron carbide particles according to claim 1, wherein the ultrasonic stirring in step S2 is performed for 1-30 min.
4. The method for preparing nano boron carbide particles according to claim 1, wherein the cooling rate in step S4 is 1-20 ℃/min.
5. The method as claimed in claim 1, wherein the gas in step S4 is one of helium and argon.
6. The method as claimed in claim 1, wherein the gas in step S4 is one of air, oxygen and carbon dioxide.
7. The method of claim 1, wherein the acid solution in step S5 is one of sulfuric acid, hydrochloric acid and nitric acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112194492A (en) * | 2020-09-15 | 2021-01-08 | 衡阳凯新特种材料科技有限公司 | Silicon nitride ceramic material, preparation method and application thereof, and bulletproof flashboard |
| CN112299850A (en) * | 2020-11-25 | 2021-02-02 | 郑州华晶实业有限公司 | High-temperature high-pressure preparation method of high-strength boron carbide ceramic |
| CN112573520A (en) * | 2020-12-29 | 2021-03-30 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanoparticles |
| CN112759408A (en) * | 2021-01-04 | 2021-05-07 | 苏州第一元素纳米技术有限公司 | Boron carbide ceramic and preparation method and application thereof |
| CN114193860A (en) * | 2021-12-16 | 2022-03-18 | 江苏上玻玻璃有限公司 | Processing technology of Low-E laminated glass |
| EP4223694A1 (en) * | 2022-02-07 | 2023-08-09 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Method of obtaining boron carbide nanoparticles |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194492A (en) * | 2020-09-15 | 2021-01-08 | 衡阳凯新特种材料科技有限公司 | Silicon nitride ceramic material, preparation method and application thereof, and bulletproof flashboard |
| CN112299850A (en) * | 2020-11-25 | 2021-02-02 | 郑州华晶实业有限公司 | High-temperature high-pressure preparation method of high-strength boron carbide ceramic |
| CN112573520A (en) * | 2020-12-29 | 2021-03-30 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanoparticles |
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| CN112759408A (en) * | 2021-01-04 | 2021-05-07 | 苏州第一元素纳米技术有限公司 | Boron carbide ceramic and preparation method and application thereof |
| CN112759408B (en) * | 2021-01-04 | 2022-12-23 | 苏州第一元素纳米技术有限公司 | Boron carbide ceramic and preparation method and application thereof |
| CN114193860A (en) * | 2021-12-16 | 2022-03-18 | 江苏上玻玻璃有限公司 | Processing technology of Low-E laminated glass |
| CN114193860B (en) * | 2021-12-16 | 2022-12-16 | 江苏上玻玻璃有限公司 | Processing technology of Low-E laminated glass |
| EP4223694A1 (en) * | 2022-02-07 | 2023-08-09 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Method of obtaining boron carbide nanoparticles |
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