CN111533131B - Based on CaCl2Preparation method of nano silicon carbide particles of shape regulator - Google Patents
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- CN111533131B CN111533131B CN202010573100.9A CN202010573100A CN111533131B CN 111533131 B CN111533131 B CN 111533131B CN 202010573100 A CN202010573100 A CN 202010573100A CN 111533131 B CN111533131 B CN 111533131B
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
Based on CaCl2A preparation method of nanometer silicon carbide particles of a shape regulator belongs to the technical field of silicon carbide preparation and aims to solve the problems of complex process, high cost, low yield and uneven granularity existing in the existing preparation of silicon carbide powder. The method comprises the following steps: firstly, preparing silicon precursor powder; secondly, uniformly mixing the silicon precursor powder and a carbon source, sintering at a high temperature, and cooling to obtain a pre-product; thirdly, washing the pre-product and then removing impurities. The invention has the beneficial effects that: using CaCl2As shape-regulating agents, the resulting CaCl-based compositions were prepared2The nanometer silicon carbide particles of the shape regulator have uniform particle size distribution and average size of 52.4 nanometers. The preparation process is complex, the cost is reduced, the process is easy to control, the production efficiency is improved, the product purity is high, the particle size distribution is uniform, and the method is suitable for industrial production. The method is applied to the preparation of the nano silicon carbide particles.
Description
Technical Field
The invention belongs to the technical field of silicon carbide preparation, and particularly relates to a CaCl-based catalyst2A method for preparing nano silicon carbide particles of a shape regulator.
Background
The silicon carbide has the excellent characteristics of light weight, high hardness, high strength, acid and alkali resistance, high temperature resistance and the like. The silicon carbide products are widely applied at present and comprise wear-resistant and heat-resistant elements, anti-corrosion materials, wastewater filtering membranes, protective armor, high-temperature wave-absorbing coatings, aerospace and the like. The sintering mechanism of the SiC block is that SiC particles are mutually attracted and bonded into small particles through heating to form a larger whole, so that the SiC ceramic obtains higher hardness and toughness. Researches show that the silicon carbide raw materials with different grain diameters have important influence on the performance of sintered products. The smaller the particle size of the silicon carbide powder raw material is, the more the morphology is close to circular particles, the more densely the gaps among the particles are filled in the sintering process, the more sufficient the mutual contact among the particles is, and the more excellent the performance of the obtained product is. The nanometer silicon carbide powder has small grain size, large specific surface area, high surface energy, great sintering activity and violent atomic diffusion at high temperature, and can inhibit the abnormal growth of crystal grains and weaken the interface combination to improve the mechanical performance of SiC ceramic. The existing process for preparing the silicon carbide powder has the defects of complex process, high equipment requirement, cost increase, low product purity, yield reduction, unstable product size and uneven particle size distribution. Therefore, the method has great significance for the research on the preparation of the nano silicon carbide particle powder.
Disclosure of Invention
The invention aims to solve the problems of complex process, high cost, low yield and non-uniform particle size of the existing preparation of silicon carbide powder, and provides a CaCl-based powder2A method for preparing nano silicon carbide particles of a shape regulator.
Based on CaCl2The preparation method of the nanometer silicon carbide particles of the shape regulator is realized according to the following steps:
firstly, preparing silicon precursor powder:
stirring and dissolving calcium chloride solid in silica sol liquid, and drying at 60-100 ℃ for 30-50 min to obtain silicon precursor powder;
secondly, placing the silicon precursor powder and the carbon source obtained in the step one into a high-speed mixer for uniformly mixing, taking out, placing into a graphite crucible, placing into a high-temperature sintering furnace under the protection of argon, heating to 850-1900 ℃, reacting for 1-9 h, and cooling to room temperature to obtain a pre-product;
thirdly, washing the pre-product obtained in the second step for 1-3 times by using an ethanol solution with the mass concentration of 20-30%, then washing for 1-3 times by using distilled water, taking out and then carrying out impurity removal treatment, namely, the CaCl-based pretreatment is completed2Preparation of nano silicon carbide particles of shape regulator.
The reaction principle of the invention is as follows: at high temperature, the carbon source generates SiO gaseous intermediate production area, enters the carbon source as a product template to generate gas-solid reaction, and uses CaCl2When used as a shape modifier, CaCl is present in the molten state2The SiO can enter the carbon template to promote the reaction of the silicon source and the carbon source, and the SiC particle product growing along the (111) crystal face of the SiC crystal growing with the lowest energy can be obtained by copying the original appearance of the carbon source.
The invention has the beneficial effects that: using CaCl2As shape-regulating agents, the resulting CaCl-based compositions were prepared2The nanometer silicon carbide particles of the shape regulator have uniform particle size distribution and average size of 52.4 nanometers. The preparation method has the advantages of simple preparation process, low cost and easily controlled process, thereby improving the production efficiency, and the product has high purity and uniform particle size distribution and is suitable for industrialized production.
The method is applied to the preparation of the nano silicon carbide particles.
Drawings
FIG. 1 is a CaCl-based alloy prepared in the examples2XRD spectrogram of the nano silicon carbide particles of the shape regulator;
FIG. 2 is a CaCl-based alloy prepared in the examples2A micro-topography of the nano-sized silicon carbide particles of the shape modifier.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: this embodiment is based on CaCl2The preparation method of the nanometer silicon carbide particles of the shape regulator is realized according to the following steps:
firstly, preparing silicon precursor powder:
stirring and dissolving calcium chloride solid in silica sol liquid, and drying at 60-100 ℃ for 30-50 min to obtain silicon precursor powder;
secondly, placing the silicon precursor powder and the carbon source obtained in the step one into a high-speed mixer for uniformly mixing, taking out, placing into a graphite crucible, placing into a high-temperature sintering furnace under the protection of argon, heating to 850-1900 ℃, reacting for 1-9 h, and cooling to room temperature to obtain a pre-product;
thirdly, washing the pre-product obtained in the second step for 1-3 times by using an ethanol solution with the mass concentration of 20-30%, then washing for 1-3 times by using distilled water, taking out and then carrying out impurity removal treatment, namely, the CaCl-based pretreatment is completed2Preparation of nano silicon carbide particles of shape regulator.
In the first step of the present embodiment, the silica sol liquid is a commercially available JN-30 type silica sol liquid.
In step two of the present embodiment, a silicon precursor powder is used as a silicon source.
The second step of the embodiment is placed into a graphite crucible, the bottom of the crucible is fully paved, and a graphite crucible cover is covered.
The purpose of the washing in step three of this embodiment is to remove the salts introduced in the reaction.
The second embodiment is as follows: the first embodiment is different from the first embodiment in that the mass ratio of the calcium chloride solid to the silica sol liquid in the first step is 1 (10-50); the stirring mode is magnetic stirring. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: in this embodiment, the carbon source in the second step is carbon black, activated carbon, carbonized lignin or carbonized fiber, which is different from the first or second embodiment. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and the first to third embodiments is that the carbon source in the second step has a particle size of 10 to 100 nm. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the present embodiment and one of the first to fourth embodiments is that the mass ratio of the silicon precursor powder to the carbon source in the second step is (1-8): 1. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that, in the second step, the parameters of the high-speed mixer are as follows: mixing for 5-10 h at a rotation speed of 60-100 r/min under the power of 1-20 Hz. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that the purity of the argon gas in the second step is 99.99%. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from the first to seventh embodiments in that the temperature rise in the second step is: heating to 800 ℃ at the speed of 5-10 ℃/min, preserving the heat at 800 ℃ for 1-3 h, and then continuously heating to 850-1900 ℃ at the speed of 1-5 ℃/min. Other steps and parameters are the same as those in one of the first to seventh embodiments.
In the embodiment, the heat preservation is carried out for 1-3 h at 800 ℃ so as to carbonize the organic solvent in the silica sol in the silicon precursor powder.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that the cooling in the second step is: cooling to 800 ℃ at the speed of 1-5 ℃/min, and then cooling to room temperature along with the furnace. Other steps and parameters are the same as those in one to eight of the embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that the impurity removal process in step three: soaking the washed product in hydrofluoric acid for 10-20 min, taking out the product, placing the product in a muffle furnace, and heating the product to 600-800 ℃ in air to burn the product for 1-6 h. Other steps and parameters are the same as those in one of the first to ninth embodiments.
The hydrofluoric acid treatment in this embodiment is intended to wash away unreacted silicon components and impurities.
The concrete implementation mode eleven: the present embodiment is quite different from the specific embodiment in that the hydrofluoric acid has a mass concentration of 40 to 44%. Other steps and parameters are the same as those in the embodiment.
The beneficial effects of the present invention are demonstrated by the following examples:
example (b):
based on CaCl2The preparation method of the nanometer silicon carbide particles of the shape regulator is realized according to the following steps:
firstly, preparing silicon precursor powder:
dissolving calcium chloride solid in silica sol liquid by magnetic stirring according to the mass ratio of 1:50, and then drying for 50min at 80 ℃ to obtain silicon precursor powder;
secondly, placing the silicon precursor powder and the carbon source obtained in the step one into a high-speed mixer, mixing uniformly, taking out, placing into a graphite crucible, placing into a high-temperature sintering furnace under the protection of argon, heating to 1700 ℃ for reaction for 2 hours, and then cooling to room temperature to obtain a pre-product;
thirdly, washing the pre-product obtained in the second step for 2 times by using an ethanol solution with the mass concentration of 25%, then washing for 2 times by using distilled water, taking out and then carrying out impurity removal treatment, namely, the CaCl-based pretreatment is completed2Preparation of nano silicon carbide particles of shape regulator.
In the first step of this example, the silica sol liquid was a commercially available JN-30 type silica sol liquid.
In the second step of this example, the carbon source is carbon black, and the particle size is 50 nm.
In the second step of this example, the mass ratio of the silicon precursor powder to the carbon source is 8: 1.
In the second step of this embodiment, parameters of the high-speed mixer are as follows: mixing for 5h at the rotation speed of 60r/min under the power of 1 Hz.
The purity of the argon in step two of this example was 99.99%.
In the second step of this embodiment, the temperature rise is: heating to 800 deg.C at a rate of 10 deg.C/min, maintaining at 800 deg.C for 1h, and heating to 1700 deg.C at a rate of 5 deg.C/min.
In the second step of this embodiment, the cooling is: cooling to 800 deg.C at a rate of 5 deg.C/min, and cooling to room temperature.
In the third step of this embodiment, the impurity removal treatment: soaking a washed product in hydrofluoric acid for treatment for 15min, taking out the product, placing the product in a muffle furnace, heating the product to 700 ℃ in air, and firing the product for 2 h; the mass concentration of the hydrofluoric acid is 40%.
In this embodiment, the silicon source mainly reacts in the form of generating a gas-phase intermediate product SiO:
SiO2(s)+Si(s)=2SiO(g)
at high temperature, the carbon source generates SiO gaseous intermediate production area, enters the carbon source as a product template to generate gas-solid reaction, and uses CaCl2When used as a shape modifier, CaCl is present in the molten state2The SiO can enter the carbon template, the reaction of the silicon source and the carbon source is promoted, and the lowest energy can be obtained by copying the original shape of the carbon sourceAnd (3) preparing SiC particle products grown on the (111) crystal face of the grown SiC crystal.
CaCl-based compositions prepared in this example2The nano silicon carbide particles of the shape regulator have an X-ray diffraction (XRD) spectrum shown in figure 1, and diffraction peaks at 35.7 degrees, 41.4 degrees, 60.0 degrees, 71.8 degrees and 75.4 degrees in the figure are respectively corresponding to (111), (200), (220), (311) and (222) crystal planes of beta-SiC; no impurity peak is found, which indicates that the method of the embodiment can successfully prepare the beta-SiC material and the product has high purity.
CaCl-based compositions prepared in this example2Nano silicon carbide particles of a shape modifier, the micro morphology thereof; as can be seen from FIG. 2, with CaCl2As a shape regulator, silicon carbide particles with uniform particle size distribution and average size of 52.4 nm can be successfully prepared.
Claims (10)
1. Based on CaCl2The preparation method of the nano silicon carbide particles of the shape regulator is characterized by comprising the following steps:
firstly, preparing silicon precursor powder:
stirring and dissolving calcium chloride solid in a silica sol liquid according to a mass ratio of 1 (10-50), and drying at 60-100 ℃ for 30-50 min to obtain silicon precursor powder;
secondly, placing the silicon precursor powder and the carbon source obtained in the step one into a high-speed mixer for uniformly mixing, taking out, placing into a graphite crucible, placing into a high-temperature sintering furnace under the protection of argon, heating to 850-1900 ℃, reacting for 1-9 h, and cooling to room temperature to obtain a pre-product;
thirdly, washing the pre-product obtained in the second step for 1-3 times by using an ethanol solution with the mass concentration of 20-30%, then washing for 1-3 times by using distilled water, taking out and then carrying out impurity removal treatment, namely, the CaCl-based pretreatment is completed2Preparation of nano silicon carbide particles of shape regulator.
2. The CaCl-based alloy according to claim 12The preparation method of the nanometer silicon carbide particles of the shape regulator is characterized in that the calcium chloride solid and the silicon in the step oneThe mass ratio of the sol liquid is 1 (10-50); the stirring mode is magnetic stirring.
3. The CaCl-based alloy according to claim 12The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that the carbon source in the step two is carbon black, activated carbon, carbonized lignin or carbonized fiber.
4. The CaCl-based alloy according to claim 12The preparation method of the shape regulator nano silicon carbide particles is characterized in that the mass ratio of the silicon precursor powder to the carbon source in the step two is (1-8): 1.
5. The CaCl-based alloy according to claim 12The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that parameters of a high-speed mixer in the step two are as follows: mixing for 5-10 h at a rotation speed of 60-100 r/min under the power of 1-20 Hz.
6. The CaCl-based alloy according to claim 12The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that the purity of the argon in the step two is 99.99 percent.
7. The CaCl-based alloy according to claim 12The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that the temperature rise in the step two is as follows: heating to 800 ℃ at the speed of 5-10 ℃/min, preserving the heat at 800 ℃ for 1-3 h, and then continuously heating to 850-1900 ℃ at the speed of 1-5 ℃/min.
8. The CaCl-based alloy according to claim 12The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that the cooling in the step two is as follows: cooling to 800 ℃ at the speed of 1-5 ℃/min, and then cooling to room temperature along with the furnace.
9. The method of claim 1Based on CaCl2The preparation method of the nanometer silicon carbide particles of the shape regulator is characterized in that the impurity removal treatment in the third step: soaking the washed product in hydrofluoric acid for 10-20 min, taking out the product, placing the product in a muffle furnace, and heating the product to 600-800 ℃ in air to burn the product for 1-6 h.
10. The CaCl-based alloy according to claim 92The preparation method of the nano silicon carbide particles of the shape regulator is characterized in that the mass concentration of hydrofluoric acid is 40-44%.
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2010085006A1 (en) * | 2009-01-20 | 2010-07-29 | The Industry & Academic Cooperation In Chungnam National University (Iac) | Fabrication method of nano-sized metal carbide powder using self-propagating high-temperature synthesis |
CN102718217A (en) * | 2012-05-18 | 2012-10-10 | 湖北大学 | High purity linear silicon carbide powder and preparation method |
CN108640117A (en) * | 2018-05-10 | 2018-10-12 | 南昌航空大学 | One kind synthesizing two dimension SiC ultrathin nanometer structures and preparation method thereof by template molten-salt growth method of graphene |
CN109879285A (en) * | 2019-03-21 | 2019-06-14 | 武汉工程大学 | A kind of silicon carbide nano material and preparation method thereof |
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WO2010085006A1 (en) * | 2009-01-20 | 2010-07-29 | The Industry & Academic Cooperation In Chungnam National University (Iac) | Fabrication method of nano-sized metal carbide powder using self-propagating high-temperature synthesis |
CN102718217A (en) * | 2012-05-18 | 2012-10-10 | 湖北大学 | High purity linear silicon carbide powder and preparation method |
CN108640117A (en) * | 2018-05-10 | 2018-10-12 | 南昌航空大学 | One kind synthesizing two dimension SiC ultrathin nanometer structures and preparation method thereof by template molten-salt growth method of graphene |
CN109879285A (en) * | 2019-03-21 | 2019-06-14 | 武汉工程大学 | A kind of silicon carbide nano material and preparation method thereof |
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Title |
---|
Molten salt synthesis and characterization of SiC coated carbon black particles for refractory castable applications;Jianke Ye et al.;《Journal of the European Ceramic Society》;20130309;第33卷;第2024页左栏第18-36行和第2026页右栏第1-5行,以及图5 * |
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Effective date of registration: 20211123 Address after: 150001 No. 92 West straight street, Harbin, Heilongjiang Patentee after: HARBIN INSTITUTE OF TECHNOLOGY Address before: 150001 room 1009, 10th floor, Science Park building, Harbin University of technology, No. 434, youyou street, Nangang District, Harbin City, Heilongjiang Province Patentee before: Heilongjiang guanci Technology Co.,Ltd. |