CN114772601A - Catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires - Google Patents
Catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires Download PDFInfo
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
Abstract
A catalyst-free controllable batch preparation method of high-strength and high-toughness boron carbide nanowires relates to a preparation method of boron carbide nanowires. The method aims to solve the problems that the boron carbide nanowire is low in purity, easy to agglomerate, difficult to remove redundant multi-walled carbon nanotubes and the like during preparation of the boron carbide nanowire. The method takes amorphous boron powder and multi-walled carbon nanotubes as raw materials, leads the multi-walled carbon nanotubes to be uniformly distributed on the surface of the amorphous boron powder through the full mixing of ball milling, and heats under the inert protective atmosphere to lead boron atoms to be diffused in the multi-walled carbon nanotubes for nucleation to generate boron carbide nanowires; removing redundant amorphous boron powder by using concentrated nitric acid, and removing redundant carbon nano tubes by using oxidizing atmosphere to finally obtain the boron carbide nano wire with high purity, good crystallinity and high mechanical strength. The method has the advantages of low cost, no participation of other catalysts, required temperature, low impurity content of the product and excellent mechanical property; the process method is simple, easy to operate and suitable for mass production.
Description
Technical Field
The invention relates to a preparation method of a boron carbide nanowire.
Background
Boron carbide, one of the common ceramic substances, has very high hardness, second only to boron nitride and diamond. As a typical ceramic with high hardness and high strength, the strength of boron carbide can reach 2500GPa, and the elastic modulus can reach 460 GPa. In addition to this, boron carbide is used by virtue of its low density (2.52 g/cm)3) Excellent in thermal expansion performance (coefficient of thermal expansion 5.73X 10)-6/° c), high-temperature conductivity, corrosion resistance, and neutron shielding properties are often used in the aerospace, nuclear engineering, and semiconductor industries. The boron carbide nanowire has excellent performance of boron carbide, and the anisotropy of the boron carbide nanowire enables the boron carbide nanowire to have good toughness. Therefore, the boron carbide nanowires are suitable for being used in composite materials such as metal matrix, ceramic matrix, polymer and the like to improve the strength and toughness of the composite materials.
At present, commercially available boron carbide at home and abroad is mainly micron boron carbide particles, and the preparation method is mainly a carbothermic method, namely, amorphous carbon and boron oxide are heated to generate oxidation-reduction reaction, and finally the boron carbide is prepared. However, the method is suitable for preparing micron-scale or nanometer-scale boron carbide particles, is generally difficult to control in the process of preparing boron carbide nanowires, and requires strict parameter control and introduction of a receiving source. Because the preparation temperature of the nanowire is lower, a catalyst is usually required to be introduced for convenient nucleation, so that the yield of the boron carbide nanowire prepared by the carbothermic method is extremely low (generally not more than 10 percent), insoluble impurities exist, the mass production is extremely difficult to realize, and the control is difficult. The key difficulty of the current boron carbide nanowire preparation is to find a novel preparation method of the boron carbide nanowire and improve the yield.
The existing literature discloses a method for generating boron carbide nanowires by reacting amorphous boron powder and multi-walled carbon nanotubes through a catalyst, but because the multi-walled carbon nanotubes are easy to agglomerate, the contact area between the multi-walled carbon nanotubes and the amorphous boron powder is easy to be insufficient, and the growth speed and the yield of the boron carbide nanowires are seriously influenced. Meanwhile, the Fe-or Ni-or Si-containing catalyst introduced due to insufficient contact cannot be removed by corrosion, resulting in insufficient purity of the nanowires. In addition, the rest carbon nanotubes are oxidized in the air at a temperature above 550 ℃, while the boron carbide has an oxidation temperature of about 450 ℃, so that the excess multi-walled carbon nanotubes are difficult to remove by burning. Therefore, how to disperse the carbon nanotubes to increase the contact area between the multiwall carbon nanotubes and the amorphous boron powder, how to prepare the boron carbide nanowires without the catalyst and increase the yield, and how to remove the redundant multiwall carbon nanotubes are difficult problems in the batch controllable preparation of the boron carbide nanowires by a template growth method.
Disclosure of Invention
The invention aims to solve the problems of low nanowire purity, easy agglomeration of carbon nanotubes, difficult removal of redundant multi-walled carbon nanotubes and the like in the preparation of the conventional boron carbide nanowire, realize the controllable growth and batch production preparation of the boron carbide nanowire, and provide the high-strength and high-toughness boron carbide nanowire (B) without a catalyst4Cnw) The controllable batch preparation method of (1).
The method comprises the steps of taking amorphous boron powder and multi-walled carbon nanotubes as raw materials, fully mixing the amorphous boron powder and the multi-walled carbon nanotubes in a ball milling mode to enable the multi-walled carbon nanotubes to be uniformly distributed on the surface of the amorphous boron powder, and then heating the amorphous boron powder in a high-temperature furnace filled with inert protective atmosphere to enable boron atoms to be diffused in the multi-walled carbon nanotubes to re-nucleate to generate boron carbide nanowires; after the boron carbide nanowires grow, removing redundant amorphous boron powder by using concentrated nitric acid, and removing redundant carbon nanotubes by using oxidizing atmosphere such as ozone and the like to finally obtain the boron carbide nanowires with high purity, good crystallinity and high mechanical strength.
The catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowires is carried out according to the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing amorphous boron powder and multi-walled carbon nanotubes in a mass ratio of 4:1, adding the amorphous boron powder and the multi-walled carbon nanotubes into a ball milling tank, adding a proper amount of ball milling balls, and performing ball milling and mixing by a certain ball milling process to obtain mixed powder;
secondly, growing the template under the condition of boron carbide nanowire high-temperature protective atmosphere
Placing the mixed powder obtained in the step one into a sintering furnace for sintering;
the sintering process comprises the following steps: rapidly heating to 1000-1200 ℃ at a speed of 10 ℃/min under an inert atmosphere, preserving heat for 2-6 h, realizing template growth of the boron carbide nanowire under a high-temperature protective atmosphere condition, finally cooling the furnace to below 120 ℃, taking out, and obtaining the low-purity boron carbide nanowire at a cooling speed of the furnace cooling not higher than 10 ℃/min;
thirdly, removing the residual amorphous boron powder and the multi-walled carbon nano-tube
Placing the low-purity boron carbide nanowire obtained in the step two in concentrated nitric acid, stirring for 2-4 h, diluting, centrifuging and drying to obtain mixed powder of the boron carbide nanowire and the multi-walled carbon nanotube; and then preserving the heat for 4-6 h at 40-80 ℃ under the condition of oxidizing atmosphere, and finally washing and drying with water or ethanol to obtain the high-purity boron carbide nanowire.
The invention has the following beneficial effects:
1. the invention takes low-price amorphous boron powder and multi-walled carbon nanotubes as raw materials, and the bulk mixing is carried out by using a ball milling mixing mode, so the cost is obviously reduced compared with other methods, the cost of the needed amorphous boron powder is only 20 ten thousand yuan per ton, and the cost of the multi-walled carbon nanotubes is only 10 ten thousand yuan per ton;
2. according to the method, the growth of the boron carbide nanowires is carried out by adopting a template growth method, other catalysts are not needed in the process, boride impurities generated by the catalyst reaction in the boron carbide nanowires are greatly reduced, and the impurity content in the grown boron carbide nanowires is lower than 0.2 wt.%. The temperature required in the growth process is only 1000-1200 ℃, which is lower than the growth temperature of other methods, and the substrate is not required to be used as a receiving source. The agglomeration of the carbon nano tubes is continuously opened by means of the shearing force between the ball-milling balls in the ball-milling process, and finally the state that the carbon nano tubes are uniformly distributed on the surface of the boron powder is realized.
3. The boron carbide nanowire grown by the method is a single crystal nanowire, the defects such as stacking faults, twin crystals and the like are few, the strength is higher than that of other methods, the nano indentation hardness can reach more than 20Gpa, and the toughness can reach 50% of bending deformation.
4. The purification process of the boron carbide nanowires is suitable for being carried out on a large scale, redundant multi-walled carbon nanotubes are oxidized by ozone under the water bath condition to form carbon dioxide to be removed, the required raw materials are common industrial raw materials, and the method can be better applied to industrial production through proper improvement.
5. The invention provides a method for preparing boron carbide nanowires with low cost, which has the advantages of simple process method, easy operation, easy control of the diameter and the length of the final boron carbide nanowires, excellent mechanical property, easy realization of industrial production and application as a reinforcement of a ceramic toughening phase and metal matrix composite.
Description of the drawings:
fig. 1 is a microstructure photograph of the boron carbide nanowires obtained in example 1.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowires is carried out according to the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing amorphous boron powder and multi-walled carbon nanotubes in a mass ratio of 4:1, adding the amorphous boron powder and the multi-walled carbon nanotubes into a ball milling tank, adding a proper amount of ball milling balls, and performing ball milling and mixing by a certain ball milling process to obtain mixed powder;
the purity of the amorphous boron powder (B) is more than 99 percent, and the purity of a multi-walled carbon nanotube (MWCNT) is more than 99 percent;
the amorphous boron powder is amorphous boron; the activity of the amorphous boron powder is higher than that of the crystalline boron powder, and the amorphous boron powder is favorable for diffusion with the multi-wall carbon nano-tube at a lower temperature. The amorphous boron powder contains the following impurities: water-soluble boron (boron oxide) not more than 0.5 wt.%, moisture not more than 0.2 wt.%, H2O2Insoluble matter does not exceed 0.1 wt.%.
Secondly, growing the template under the condition of boron carbide nanowire high-temperature protective atmosphere
Placing the mixed powder obtained in the step one into a sintering furnace for sintering;
the sintering process comprises the following steps: rapidly heating to 1000-1200 ℃ at a speed of 10 ℃/min in an inert atmosphere, preserving heat for 2-6 h to realize template growth of the boron carbide nanowires under a high-temperature protective atmosphere condition, finally cooling the furnace to below 120 ℃, taking out the boron carbide nanowires, and obtaining the low-purity boron carbide nanowires, wherein the cooling speed of the furnace cooling is not higher than 10 ℃/min;
the mixed powder can be added into a graphite tank when being sintered, and a sintering furnace can be a vacuum atmosphere box furnace; and placing the graphite tank covered with the graphite cover in the center of a hearth of the high-temperature vacuum atmosphere box-type furnace. After the furnace door is closed, the air pressure in the furnace is pumped to be below 100Pa by using a vacuum pump, protective gas is introduced until the gas pressure reaches 0.1MPa, and the protective gas is repeatedly introduced for three times to fill the argon in the furnace body; the graphite tank is made of isostatic pressing graphite, and the graphite cover is well matched with the graphite tank. The volume of the powder should not exceed 1/3 the volume of the graphite can. The heating temperature range of the vacuum atmosphere box-type furnace is 0-1400 ℃, the internal pressure range is 0-1 MPa, and the furnace body is made of high-alumina bricks.
Thirdly, removing the residual amorphous boron powder and the multi-walled carbon nano-tube
Placing the low-purity boron carbide nanowires obtained in the second step into concentrated nitric acid, stirring for 2-4 h, removing the residual amorphous boron powder, and increasing the surface defects of the residual multi-walled carbon nanotubes; after dilution, centrifuging and drying to obtain mixed powder of the boron carbide nanowire and the multi-walled carbon nanotube; then preserving the heat for 4-6 hours at 40-80 ℃ under the condition of oxidizing atmosphere, and placing the mixture in a wide-mouth bottle and performing the heat preservation under the water bath condition of 40-80 ℃; the boron carbide nanowire with the surface coated by the boron oxide thin layer is obtained; finally, washing and drying the boron carbide nano wire by water or ethanol to obtain a high-purity boron carbide nano wire; the washing steps of water or ethanol are as follows: adding the powder into water or ethanol, stirring, and removing liquid substances by suction filtration.
The embodiment has the following beneficial effects:
1. in the embodiment, the low-price amorphous boron powder and the multi-walled carbon nanotubes are used as raw materials, and are mixed in batch in a ball milling mixing mode, so that the cost is obviously reduced compared with other methods, the cost of the needed amorphous boron powder is only 20 ten thousand yuan per ton, and the cost of the multi-walled carbon nanotubes is only 10 ten thousand yuan per ton;
2. in the embodiment, the growth of the boron carbide nanowires is carried out by adopting a template growth method, other catalysts are not needed in the process, boride impurities generated by the catalyst reaction in the boron carbide nanowires are greatly reduced, and the impurity content in the grown boron carbide nanowires is lower than 0.2 wt.%. The temperature required in the growth process is only 1000-1200 ℃, which is lower than the growth temperature of other methods, and the substrate is not required to be used as a receiving source. The agglomeration of the carbon nano tubes is continuously opened by means of the shearing force between the ball grinding balls in the ball grinding process, and finally the state that the carbon nano tubes are uniformly distributed on the surface of the boron powder is realized.
3. The boron carbide nanowire grown in the embodiment is a single crystal nanowire, the defects such as stacking faults, twin crystals and the like are few, the strength is higher than that of other methods, the nanoindentation hardness can reach more than 20Gpa, and the toughness can reach 50% of bending deformation.
4. In the embodiment, the purification process of the boron carbide nanowires is suitable for being carried out on a large scale, redundant multi-walled carbon nanotubes are oxidized by ozone under the water bath condition to form carbon dioxide to be removed, and the required raw materials are common industrial raw materials and can be better applied to industrial production through proper improvement.
5. The embodiment provides a method for preparing the boron carbide nanowires with low cost, the process method is simple and easy to operate, the diameter and the length of the final boron carbide nanowires are easy to control, the mechanical property is excellent, the industrial production is easy to realize, and the boron carbide nanowires can be applied as a reinforcement of a ceramic toughening phase and metal matrix composite material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 to 2 mu m.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: firstly, the outer diameter of the multi-wall carbon nano tube is 8-150 nm, the inner diameter is 4-30 nm, and the length is 5-20 mu m; the average outer diameter is 20nm to 100nm, the average inner diameter is 6nm to 25nm, and the average length is 10 mu m.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is: step one, the ball milling and mixing process comprises the following steps: ball-milling at the rotating speed of 100-200 rpm for 4-10 h at the ball-milling ratio of (5-20): 1, pausing for 5 minutes after each ball-milling for 10 minutes during the ball-milling period, pausing for 5 minutes after reverse ball-milling for 10 minutes, sieving to obtain 150-300-mesh mixed powder after the ball-milling is finished, and ensuring sufficient porosity in the powder through sieving; the diameters of the ball grinding balls are 3mm and 5mm, and the mass ratio of the ball grinding balls with the two diameters is 1: 1.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the first step, the multi-walled carbon nanotube may be a conventional multi-walled carbon nanotube without hydroxylation or carboxylation, or a hydroxylated multi-walled carbon nanotube or a carboxylated multi-walled carbon nanotube. The impurity content in conventional multi-walled carbon nanotubes does not exceed 0.5 wt.%; the hydroxyl content in the hydroxylated multi-wall carbon nano-tube is 3 wt.%, and the content of impurity elements does not exceed 0.5 wt.%; the carboxyl content in the carboxylated multi-wall carbon nano tube is 5 wt.%, and the content of impurity elements does not exceed 0.5 wt.%. The presence of carboxyl or hydroxyl groups in the multi-walled carbon nanotubes increases yield because the carboxyl or hydroxyl groups disappear under high temperature conditions to form vacancies to facilitate nanowire growth.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step two, the inert atmosphere is argon, helium and other inert gas atmosphere, the impurity content of the inert gas is not more than 0.1 wt.%, and the speed of introducing the inert gas into the furnace body is 0.5-1L/min. Nitrogen cannot be used as a shielding gas.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and step three, the molar concentration of the nitric acid in the concentrated nitric acid is 4-12 mol/L. The impurity content does not exceed 0.1 wt.%, and the remaining component is water.
The specific implementation mode eight: the present embodiment differs from one of the first to seventh embodiments in that: and stirring in the third step by using a mechanical stirring device at the stirring speed of 100-500 rpm, wherein the temperature is required to be kept not more than 60 ℃ in the stirring process so as to avoid the decomposition and volatilization of the concentrated nitric acid.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: thirdly, selecting strong oxidizing gas such as mixed gas of air and ozone in the oxidizing atmosphere, wherein the gas flow rate is 3-9L/min; the content of ozone in the mixed gas of air and ozone was 5 g/L.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that: and step three, the centrifugation speed is 2500-3500 rpm.
Example 1: the catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowire is carried out according to the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing 12g of amorphous boron powder and 3g of multi-walled carbon nanotubes (not hydroxylated or carboxylated), adding into a 250ml zirconia ball-milling tank, adding 100g of zirconia ball-milling balls with the diameter of 3mm and 100g of zirconia ball-milling balls with the diameter of 5mm, and ball-milling at the rotating speed of 100rpm for 4 hours;
the purity of the amorphous boron powder (B) is more than 99 percent, and the purity of the multi-wall carbon nano tube is more than 99 percent; the amorphous boron powder is amorphous boron, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 mu m; the outer diameter of the multi-wall carbon nano tube is 8-30 nm, the inner diameter of the multi-wall carbon nano tube is 4-8 nm, the length of the multi-wall carbon nano tube is 5-20 mu m, the average outer diameter is 20nm, the average inner diameter is 6nm, and the average length is 10 mu m. Suspending for 5 minutes after ball milling for 10min in the ball milling period, performing reverse ball milling for 5 minutes after 10min, and sieving to obtain mixed powder of 300 meshes;
the amorphous boron powder is amorphous boron; the activity of the amorphous boron powder is higher than that of the crystalline boron powder, and the amorphous boron powder is favorable for diffusion with the multi-wall carbon nano tube at a lower temperature. The impurities contained in the amorphous boron powder are: water-soluble boron (boron oxide) not more than 0.5 wt.%, moisture not more than 0.2 wt.%, H2O2Insoluble matter does not exceed 0.1 wt.%.
Secondly, growing the template under the condition of high-temperature protective atmosphere of the boron carbide nanowire
And (3) adding the mixed powder of the amorphous boron powder and the multi-walled carbon nano tubes subjected to ball milling in the step one into a graphite tank, and placing the graphite tank covered with a graphite cover in the center of a hearth of a high-temperature vacuum atmosphere box-type furnace. After the furnace door is closed, the vacuum pump is utilized to pump the pressure in the furnace to be below 100Pa, then protective gas is introduced to 0.1MPa, and the process is repeated for three times to fill the argon in the furnace body. Rapidly heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 4h, taking out after furnace cooling is carried out to below 120 ℃, and obtaining the low-purity boron carbide nanowire, wherein the cooling speed of the furnace cooling is not higher than 10 ℃/min;
thirdly, removing the residual amorphous boron powder and the multi-wall carbon nano-tube
Placing the low-purity boron carbide nanowires obtained in the step two in concentrated nitric acid with the molar concentration of 12mol/L, and slightly stirring for 4 hours by using a mechanical stirring device; the stirring speed is 150rpm, and the temperature is required to be kept not more than 60 ℃ in the stirring process; after dilution, centrifuging and drying, putting the powder into a wide-mouth bottle under the condition of 80 ℃ water bath, continuously introducing ozone-oxygen mixed gas with the ozone concentration of 5g/L, and preserving heat for 6 hours; and washing and drying the obtained powder to obtain the high-purity boron carbide nanowire.
The method has the advantages of low cost, no need of participation of other catalysts and required temperature, low impurity content of the product and excellent mechanical property; the process method is simple, easy to operate and suitable for mass production; fig. 1 is a microstructure photograph of the boron carbide nanowires obtained in example 1. It can be seen that the nanowires obtained in example 1 are rod-shaped, and have a diameter of 40 to 80nm, an average diameter of 60nm, a length of 1 to 10 μm, and an average length of 5 μm. The nano indentation hardness is 20.5GPa, the bending toughness can reach 52.6 percent, and the impurity content is lower than 0.2 wt.%.
Example 2: the catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowires of the embodiment comprises the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing 12g of amorphous boron powder and 3g of multi-walled carbon nanotubes (not hydroxylated or carboxylated), adding into a 250ml zirconia ball-milling tank, adding 100g of zirconia ball-milling balls with the diameter of 3mm and 100g of zirconia ball-milling balls with the diameter of 5mm, and ball-milling at the rotating speed of 100rpm for 4 hours;
the purity of the amorphous boron powder (B) is more than 99 percent, and the purity of the multi-wall carbon nano tube is more than 99 percent; the amorphous boron powder is amorphous boron, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 mu m; the multi-wall carbon nano tube has the outer diameter of 50-150 nm, the inner diameter of 20-30 nm, the length of 5-20 mu m, the average outer diameter of 100nm, the average inner diameter of 25nm and the average length of 10 mu m. Pausing for 5 minutes after ball milling is carried out for 10 minutes in the ball milling period, pausing for 5 minutes after ball milling is carried out for 10 minutes in a reverse direction, and sieving to obtain mixed powder of 300 meshes;
the amorphous boron powder is amorphous boron; the activity of the amorphous boron powder is higher than that of the crystalline boron powder, and the amorphous boron powder is favorable for diffusion with the multi-wall carbon nano tube at a lower temperature. The impurities contained in the amorphous boron powder are: water-soluble boron (boron oxide) not more than 0.5 wt.%, moisture not more than 0.2 wt.%, H2O2Insoluble matter does not exceed 0.1 wt.%.
Secondly, growing the template under the condition of high-temperature protective atmosphere of the boron carbide nanowire
And D, adding the mixed powder of the amorphous boron powder and the multi-walled carbon nano tubes subjected to ball milling in the step one into a graphite tank, and placing the graphite tank covered with a graphite cover in the center of a hearth of a high-temperature vacuum atmosphere box-type furnace. After the furnace door is closed, the vacuum pump is utilized to pump the pressure in the furnace to be below 100Pa, then protective gas is introduced to 0.1MPa, and the process is repeated for three times to fill the argon in the furnace body. Rapidly heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining for 4 hr, cooling to below 120 deg.C, taking out, and cooling at a speed of no higher than 10 deg.C/min; obtaining the low-purity boron carbide nanowire;
thirdly, removing the residual amorphous boron powder and the multi-wall carbon nano-tube
Placing the low-purity boron carbide nanowires obtained in the second step into concentrated nitric acid with the molar concentration of 12mol/L, and lightly stirring for 4 hours by using a mechanical stirring device; the stirring speed is 150rpm, and the temperature is required to be kept not more than 60 ℃ in the stirring process; after dilution, centrifuging and drying, putting the powder into a wide-mouth bottle under the condition of 80 ℃ water bath, continuously introducing ozone-oxygen mixed gas, keeping the concentration of ozone at 5g/L, and keeping the temperature for 6 hours; and washing and drying the obtained powder to obtain the high-purity boron carbide nanowire.
The method has the advantages of low cost, no need of participation of other catalysts and required temperature, low impurity content of the product and excellent mechanical property; the process method is simple, easy to operate and suitable for mass production; the diameter of the nanowire obtained in example 2 is 70 to 250nm, the average diameter is 150nm, the length is 1 to 10 μm, and the average length is 5 μm. The nano indentation hardness is 20.0GPa, the bending toughness can reach 40.6 percent, and the impurity content is lower than 0.2 wt.%.
Example 3: the catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowires of the embodiment comprises the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing 12g of amorphous boron powder and 3g of multi-walled carbon nanotubes (not hydroxylated or carboxylated), adding into a 250ml zirconia ball-milling tank, adding 100g of zirconia ball-milling balls with the diameter of 3mm and 100g of zirconia ball-milling balls with the diameter of 5mm, and ball-milling at the rotating speed of 100rpm for 4 hours;
the purity of the amorphous boron powder (B) is more than 99 percent, and the purity of the multi-wall carbon nano tube is more than 99 percent; the amorphous boron powder is amorphous boron, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 mu m; the outer diameter of the multi-wall carbon nano tube is 8-30 nm, the inner diameter of the multi-wall carbon nano tube is 4-8 nm, the length of the multi-wall carbon nano tube is 5-20 mu m, the average outer diameter is 20nm, the average inner diameter is 6nm, and the average length is 10 mu m. Pausing for 5 minutes after ball milling is carried out for 10 minutes in the ball milling period, pausing for 5 minutes after ball milling is carried out for 10 minutes in a reverse direction, and sieving to obtain mixed powder of 300 meshes;
the amorphous boron powder is amorphous boron; the activity of the amorphous boron powder is higher than that of the crystalline boron powder, and the amorphous boron powder is favorable for diffusion with the multi-wall carbon nano-tube at a lower temperature. The amorphous boron powder contains the following impurities: water-soluble boron (boron oxide) not more than 0.5 wt.%, moisture not more than 0.2 wt.%, H2O2Insoluble matter does not exceed 0.1 wt.%.
Secondly, growing the template under the condition of boron carbide nanowire high-temperature protective atmosphere
And (3) adding the mixed powder of the amorphous boron powder and the multi-walled carbon nano tubes subjected to ball milling in the step one into a graphite tank, and placing the graphite tank covered with a graphite cover in the center of a hearth of a high-temperature vacuum atmosphere box-type furnace. After the furnace door is closed, the vacuum pump is utilized to pump the pressure in the furnace to be below 100Pa, then protective gas is introduced to 0.5MPa, and the process is repeated for three times to fill the argon in the furnace body. Rapidly heating to 1100 ℃ at the speed of 10 ℃/min, preserving heat for 6 hours, taking out after furnace cooling is carried out to the temperature of below 120 ℃, and obtaining the low-purity boron carbide nanowire when the cooling speed of the furnace cooling is not higher than 10 ℃/min;
thirdly, removing the residual amorphous boron powder and the multi-wall carbon nano-tube
Placing the low-purity boron carbide nanowires obtained in the step two in concentrated nitric acid with the molar concentration of 12mol/L, and slightly stirring for 4 hours by using a mechanical stirring device; the stirring speed is 150rpm, and the temperature is required to be kept not more than 60 ℃ in the stirring process; after dilution, centrifuging and drying, putting the powder into a wide-mouth bottle under the condition of 80 ℃ water bath, continuously introducing ozone-oxygen mixed gas, keeping the concentration of ozone at 5g/L, and keeping the temperature for 6 hours; and washing and drying the obtained powder to obtain the high-purity boron carbide nanowire.
The method has the advantages of low cost, no need of participation of other catalysts and required temperature, low impurity content of the product and excellent mechanical property; the process method is simple, easy to operate and suitable for mass production; the diameter of the nanowire obtained in example 3 is 40-120 nm, the average diameter is 80nm, the length is 0.5-3 μm, and the average length is 2 μm. The nano indentation hardness is 21GPa, the bending toughness can reach 22.8 percent, and the impurity content is lower than 0.2 wt.%.
Example 4: the catalyst-free controllable batch preparation method of the high-strength high-toughness boron carbide nanowires of the embodiment comprises the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing 12g of amorphous boron powder and 3g of hydroxylated multi-walled carbon nanotubes, adding the amorphous boron powder and the hydroxylated multi-walled carbon nanotubes into a 250ml zirconia ball-milling tank, adding 100g of zirconia ball-milling balls with the diameter of 3mm and 100g of zirconia ball-milling balls with the diameter of 5mm, and carrying out ball-milling at the rotating speed of 100rpm for 4 hours;
the purity of the amorphous boron powder (B) is more than 99 percent, the purity of the multi-wall carbon nano tube is more than 95 percent, and the rest part is hydroxyl; the amorphous boron powder is amorphous boron, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 mu m; the multi-wall carbon nano tube has the outer diameter of 50-150 nm, the inner diameter of 20-30 nm, the length of 5-20 mu m, the average outer diameter of 100nm, the average inner diameter of 25nm and the average length of 10 mu m. Pausing for 5 minutes after ball milling is carried out for 10 minutes in the ball milling period, pausing for 5 minutes after ball milling is carried out for 10 minutes in a reverse direction, and sieving to obtain mixed powder of 300 meshes;
the amorphous boron powder is amorphous boron; the activity of the amorphous boron powder is higher than that of the crystalline boron powder, and the amorphous boron powder is favorable for diffusion with the multi-wall carbon nano tube at a lower temperature. The amorphous boron powder contains the following impurities: water-soluble boron (boron oxide) not more than 0.5 wt.%, moisture not more than 0.2 wt.%, H2O2Insoluble matter does not exceed 0.1 wt.%.
Secondly, growing the template under the condition of boron carbide nanowire high-temperature protective atmosphere
And (3) adding the mixed powder of the amorphous boron powder and the multi-walled carbon nano tubes subjected to ball milling in the step one into a graphite tank, and placing the graphite tank covered with a graphite cover in the center of a hearth of a high-temperature vacuum atmosphere box-type furnace. After the furnace door is closed, the air pressure in the furnace is pumped to be below 100Pa by using a vacuum pump, then protective gas is introduced to 0.1MPa, and the process is repeated for three times to fill argon in the furnace body. Rapidly heating to 1000 deg.C at a speed of 10 deg.C/min, maintaining for 4 hr, cooling to below 120 deg.C, taking out, and cooling at a speed of no higher than 10 deg.C/min; obtaining the low-purity boron carbide nanowire;
thirdly, removing residual amorphous boron powder and multi-wall carbon nano-tubes
Placing the low-purity boron carbide nanowires obtained in the second step into concentrated nitric acid with the molar concentration of 12mol/L, and lightly stirring for 4 hours by using a mechanical stirring device; the stirring speed is 150rpm, and the temperature is required to be kept not more than 60 ℃ in the stirring process; after dilution, centrifuging and drying, putting the powder into a wide-mouth bottle under the condition of 80 ℃ water bath, continuously introducing ozone-oxygen mixed gas, keeping the concentration of ozone at 5g/L, and keeping the temperature for 6 hours; and washing and drying the obtained powder to obtain the high-purity boron carbide nanowire.
The method has the advantages of low cost, no participation of other catalysts, required temperature, low impurity content of the product and excellent mechanical property; the process method is simple, easy to operate and suitable for mass production; the diameter of the nanowire obtained in example 4 is 40 to 120nm, the average diameter is 80nm, the length is 0.5 to 3 μm, and the average length is 2 μm. The nano indentation hardness is 21GPa, the bending toughness can reach 40.6 percent, and the impurity content is lower than 0.2 wt.%.
Claims (10)
1. A catalyst-free controllable batch preparation method of high-strength and high-toughness boron carbide nanowires is characterized by comprising the following steps: the method comprises the following steps:
ball milling and mixing of boron carbide nanowire preparation raw materials
Weighing amorphous boron powder and multi-walled carbon nanotubes in a mass ratio of 4:1, adding the amorphous boron powder and the multi-walled carbon nanotubes into a ball milling tank, adding a proper amount of ball milling balls, and performing ball milling and mixing by a certain ball milling process to obtain mixed powder;
secondly, growing the template under the condition of high-temperature protective atmosphere of the boron carbide nanowire
Placing the mixed powder obtained in the step one into a sintering furnace for sintering;
the sintering process comprises the following steps: rapidly heating to 1000-1200 ℃ at a speed of 10 ℃/min in an inert atmosphere, preserving heat for 2-6 h to realize template growth of the boron carbide nanowires under a high-temperature protective atmosphere condition, finally cooling the furnace to below 120 ℃, taking out the boron carbide nanowires, and obtaining the low-purity boron carbide nanowires, wherein the cooling speed of the furnace cooling is not higher than 10 ℃/min;
thirdly, removing the residual amorphous boron powder and the multi-walled carbon nano-tube
Placing the low-purity boron carbide nanowire obtained in the step two in concentrated nitric acid, stirring for 2-4 h, diluting, centrifuging and drying to obtain mixed powder of the boron carbide nanowire and the multi-walled carbon nanotube; and then preserving the heat for 4-6 h at 40-80 ℃ under the condition of oxidizing atmosphere, and finally washing and drying with water or ethanol to obtain the high-purity boron carbide nanowire.
2. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: step one, the diameter of the amorphous boron powder is distributed between 200nm and 5 mu m, and the average diameter is 1 to 2 mu m.
3. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: step one, the outer diameter of the multi-wall carbon nano tube is 8-150 nm, the inner diameter of the multi-wall carbon nano tube is 4-30 nm, and the length of the multi-wall carbon nano tube is 5-20 mu m; the average outer diameter is 20nm to 100nm, the average inner diameter is 6nm to 25nm, and the average length is 10 mu m.
4. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: step one, the ball milling and mixing process comprises the following steps: ball-milling at a rotation speed of 100-200 rpm for 4-10 h at a ball-material ratio of (5-20): 1, pausing for 5 minutes after each ball-milling for 10 minutes during the ball-milling period, pausing for 5 minutes after reverse ball-milling for 10 minutes, and sieving to obtain 150-300 mesh mixed powder after the ball-milling is completed; the diameters of the ball grinding balls are 3mm and 5mm, and the mass ratio of the ball grinding balls with the two diameters is 1: 1.
5. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: in the first step, the multi-walled carbon nano-tube is a conventional multi-walled carbon nano-tube which is not hydroxylated or carboxylated, or a hydroxylated multi-walled carbon nano-tube or a carboxylated multi-walled carbon nano-tube.
6. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: and the inert atmosphere in the second step is argon atmosphere or helium atmosphere.
7. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: thirdly, the molar concentration of nitric acid in the concentrated nitric acid is 4-12 mol/L; the impurity content does not exceed 0.1 wt.%, and the remaining component is water.
8. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: and stirring in the third step by using a mechanical stirring device at the stirring speed of 100-500 rpm, wherein the temperature is required to be kept not more than 60 ℃ in the stirring process so as to avoid the decomposition and volatilization of the concentrated nitric acid.
9. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: thirdly, the oxidizing atmosphere is a mixed gas of air and ozone or ozone, and the gas flow rate is 3-9L/min; the content of ozone in the mixed gas of air and ozone was 5 g/L.
10. The catalyst-free controllable batch preparation method of high-strength high-toughness boron carbide nanowires according to claim 1, characterized in that: and step three, the centrifugation speed is 2500-3500 rpm.
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| JP2004161560A (en) * | 2002-11-14 | 2004-06-10 | National Institute For Materials Science | Manufacturing process of boron carbide nanowire |
| CN112794330A (en) * | 2021-01-18 | 2021-05-14 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanowires |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004161560A (en) * | 2002-11-14 | 2004-06-10 | National Institute For Materials Science | Manufacturing process of boron carbide nanowire |
| CN112794330A (en) * | 2021-01-18 | 2021-05-14 | 黑龙江冠瓷科技有限公司 | Preparation method of boron carbide nanowires |
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