CN110668447B - Synthesis method of silicon carbide nanowire - Google Patents
Synthesis method of silicon carbide nanowire Download PDFInfo
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- CN110668447B CN110668447B CN201911054722.4A CN201911054722A CN110668447B CN 110668447 B CN110668447 B CN 110668447B CN 201911054722 A CN201911054722 A CN 201911054722A CN 110668447 B CN110668447 B CN 110668447B
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Abstract
A method for synthesizing silicon carbide nano-wires relates to a method for synthesizing silicon carbide nano-wires. The invention aims to solve the technical problems of serious raw material waste, high cost, uneven structure and low length-diameter ratio of the existing method for preparing the silicon carbide nanowire. The method comprises the following steps: and placing the treated growth substrate above the silicon resin in the crucible, placing the crucible in a vacuum high-temperature furnace, heating, preserving heat and cooling to obtain the silicon-based growth substrate. The method can greatly improve the utilization rate of raw materials so as to reduce the cost while growing the SiC nanowires and generate SiC nanoparticles in the die, and the special chain bead-shaped structure ensures that the SiC nanowires have greater application potential in composite materials, field emitters, photocatalysts, hydrogen storage and hydrophobic surfaces. The generation of the chain bead-shaped nanowire is simultaneously accompanied with the generation of the overlong and overlong SiC nanowire. The product structure is uniform. The invention belongs to the field of preparation of nanowires.
Description
Technical Field
The invention relates to a method for synthesizing a silicon carbide nanowire.
Background
Silicon carbide as a third-generation semiconductor material has characteristics such as a wide band gap, high thermal conductivity, large electron saturation mobility, and good chemical stability, compared with a first-generation semiconductor represented by a silicon semiconductor and a second-generation semiconductor represented by a gallium arsenide (GaAs) semiconductor. Has good conductivity, toughness, high temperature resistance, corrosion resistance, abrasion resistance, radiation resistance and other properties. In addition to the above properties, one-dimensional (1D) SiC nanomaterials, which exhibit unique mechanical, electrical and optical properties, have attracted considerable attention from a large number of researchers, have found widespread use in composites, field emitters, optical circuits, light emitting diodes, photocatalysts, hydrogen storage and hydrophobic surfaces. The breaking strength of the SiC nanowire is far greater than that of bulk SiC and micron-sized SiC whiskers, so that the SiC nanowire has more excellent performance in application to composite materials.
At present, a plurality of methods for synthesizing the silicon carbide nanowires are available, and mainly comprise a carbothermic method, a template growth method, a chemical vapor deposition method and the like. The major mechanisms for synthesizing silicon carbide whiskers include a VLS mechanism and a VL mechanism, and the major differences are that the VLS method uses a catalyst with appropriate composition and performance, so that the nanowires grow at a high speed and at a low temperature, which causes a problem that the product needs to be subjected to a one-step catalyst separation operation. In contrast, the VL reaction mechanism has a slow growth rate and a high growth temperature, which has the advantage that the product is relatively pure without the need for catalyst separation. The research shows that two growth mechanisms of VLS and VL exist in the growth process of the nanowire added with the metal catalyst. As it is found in SEM electron micrographs, the phenomenon of no metal droplets at the nanowire tips occurs.
At present, the growth of the nanowire is still in a laboratory stage for various reasons, the problems of small length-diameter ratio, uneven morphology and structure and the like generally exist in the SiC nanowire synthesized by researchers at present, the growth of the nanowire is mostly carried out by adopting a gas phase method at present, the yield is low, the residual raw material slag for growing the SiC nanowire cannot be well applied, the raw material waste is serious, and the economic cost is high. Which makes the industrialization promotion difficult.
Disclosure of Invention
The invention aims to solve the technical problems of serious raw material waste, high cost, non-uniform structure and low length-diameter ratio of the existing method for preparing the silicon carbide nanowire, and provides a method for synthesizing the silicon carbide nanowire.
The synthesis method of the silicon carbide nanowire comprises the following steps:
firstly, weighing silicon resin and a metal catalyst, and putting the silicon resin into a crucible;
dissolving a metal catalyst by using absolute ethyl alcohol, wherein the concentration of the catalyst is 0.01-0.2mol/L, and obtaining a metal salt solution;
respectively cleaning the growth substrate with distilled water and ethanol, drying in vacuum, putting the dried growth substrate in a metal salt solution, soaking for 30min-2h at 20 ℃ under vacuum, and then drying the soaked growth substrate at 60-80 ℃ under vacuum;
fourthly, the growth substrate processed in the third step is placed above the silicon resin in the crucible, the crucible is placed in a vacuum high-temperature furnace, under the conditions that the heating rate is 1-10 ℃/min and the argon protection is carried out, the temperature is raised to 1300-1700 ℃, the temperature is kept for 1-5h, the temperature is lowered, the temperature lowering rate is set to be two hours and is lowered to 1000 ℃, and then the silicon carbide nanowire is obtained after natural cooling to the room temperature.
The silicone resin is polymethyl silsesquioxane, methyl phenyl silicone resin, methyl silicone resin, low phenyl methyl silicone resin, self-drying silicone resin, high-temperature silicone resin, epoxy modified silicone resin, silicone polyester modified resin, self-drying environment-friendly silicone resin, non-stick coating MQ material silicone resin, highlight silicone resin, benzyl transparent silicone resin, methyl transparent silicone resin, mica bonding silicone resin, polymethyl silicone resin, amino silicone resin, fluorosilicone resin, silicone-epoxy resin, silicone polyester resin, solvent-resistant silicone resin, silicone resin adhesive, high-temperature-resistant methyl silicone resin, methyl MQ silicone resin or vinyl MQ silicone resin.
Step one, the metal catalyst is Fe (CO)5、Fe2(CO)9、Fe(C5H5)、Fe3O4、FeCl2、FeCl2·6H2O、FeCl3、FeCl3·6H2O、Fe(NO)2、Fe(NO)3、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO)4、Ni(NO3)2、CuCl2、Cu(NO3)2Copper naphthenate C22H14CuO4、Cu2O、Mn(NO3)2Manganese stearate (C)17H35COO)2Mn、PdCl2、Y2O3、DyCl3、CoC2O4、CoCO3、CoO、CoCl2、Co(OH)2、Co(NH3)6、Co(CN)6、Co(SCN)4、Co(CO)4、Co(NO3)2。
Step one, the crucible is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible or a silicon carbide crucible;
step three, the growth substrate is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3。
The synthesis method of the silicon carbide nanowire comprises the following steps:
weighing silicon resin and a metal catalyst, mixing to obtain a mixture, wherein the mass fraction of the metal catalyst in the mixture is 1-10%, and putting the mixture into a crucible;
and secondly, respectively cleaning the growth substrate by using distilled water and ethanol, drying the growth substrate in vacuum at the temperature of 20-60 ℃, placing the dried growth substrate on the mixture in the crucible, then placing the crucible in a vacuum high-temperature furnace, heating the crucible to 1300-1700 ℃ under the conditions of heating rate of 1-10 ℃/min and argon protection, preserving the temperature for 1-5h, cooling the crucible, setting the cooling rate for two hours, cooling the temperature to 1000 ℃, and naturally cooling the crucible to room temperature to obtain the silicon carbide nanowire.
Step one, the silicon resin is polymethyl silsesquioxane, methyl phenyl silicon resin, methyl silicon resin, low phenyl methyl silicon resin, self-drying type organic silicon resin, high-temperature type organic silicon resin, epoxy modified organic silicon resin, organic silicon polyester modified resin, self-drying type environment-friendly organic silicon resin, non-stick coating MQ material organic silicon resin, highlight organic silicon resin, benzyl transparent silicon resin, methyl transparent organic silicon resin, mica bonding silicon resin, polymethyl silicon resin, amino silicon resin, fluorine silicon resin, organic silicon-epoxy resin, organic silicon polyester resin, solvent-resistant type organic silicon resin, organic silicon resin adhesive, high-temperature resistant methyl silicon resin, methyl MQ silicon resin or vinyl MQ silicon resin;
step one, the metal catalyst is Fe (CO)5、Fe2(CO)9、Fe(C5H5)、Fe3O4、FeCl2、FeCl2·6H2O、FeCl3、FeCl3·6H2O、Fe(NO)2、Fe(NO)3、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO)4、Ni(NO3)2、CuCl2、Cu(NO3)2Copper naphthenate C22H14CuO4、Cu2O、Mn(NO3)2Manganese stearate (C)17H35COO)2Mn、PdCl2、Y2O3、DyCl3、CoC2O4、CoCO3、CoO、CoCl2、Co(OH)2、Co(NH3)6、Co(CN)6、Co(SCN)4、Co(CO)4、Co(NO3)2；
Step one, the crucible is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible or a silicon carbide crucible;
the growth substrate in the second step is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3。
The principle of the invention is that the high polymerization degree silicon resin is cracked under the high temperature condition to generate gases such as SiO, CO and the like, the metal salt is gasified under the high temperature condition, the reducing gases such as CO, SiO and the like reduce metal ions into simple substance metal, the metal is in a liquid state under the high temperature condition, liquid metal drops continuously absorb CO (g), SiO (g) and Si (g) in a system, and the gas absorbed on the metal drops reacts to generate SiC nano wires. According to the invention, by reasonably adjusting the raw material proportion and the temperature condition, the growth of SIC nanowires with special shapes is realized, and silicon carbide particles with uniform particle sizes are prepared at the bottom of the die. The invention is expected to be produced in industrialization. And the special appearance of the SiC nanowire can ensure that the SiC nanowire is expected to show more excellent performances on composite materials, field emitters, photocatalysts, hydrogen storage and hydrophobic surfaces.
The invention aims to provide a method for preparing a silicon carbide nanowire, which can generate SiC nanoparticles in a die while growing the SiC nanowire, so that the utilization rate of raw materials can be greatly improved, the cost is reduced, and a good prospect is brought to popularization of the SiC nanowire. Meanwhile, the chain bead-shaped SiC nanowire is synthesized, and the special chain bead-shaped structure enables the SiC nanowire to have greater application potential in composite materials, field emitters, photocatalysts, hydrogen storage and hydrophobic surfaces. The generation of the chain bead-shaped nanowire is simultaneously accompanied with the generation of the overlong and overlong SiC nanowire. The product has uniform structure, and has more excellent application potential in composite materials, field emitters, optical circuits, light-emitting diodes, photocatalysts, hydrogen storage and hydrophobic surfaces.
Drawings
FIG. 1 is a low magnification SEM image of a mold internally grown SiC nanosphere of experiment one;
FIG. 2 is a high magnification SEM image of a mold internally grown SiC nanosphere of experiment one;
FIG. 3 is an SEM image of SiC nanowires grown on a growth substrate in experiment one;
fig. 4 is an XRD spectrum of the SiC nanowire obtained in experiment one;
FIG. 5 is a high magnification SEM image of the SiC nanospheres obtained in experiment two;
fig. 6 is an XRD spectrum of the SiC nanowire obtained in experiment two.
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: the synthesis method of the silicon carbide nanowire in the embodiment is carried out according to the following steps:
firstly, weighing silicon resin and a metal catalyst, and putting the silicon resin into a crucible;
dissolving a metal catalyst by using absolute ethyl alcohol, wherein the concentration of the catalyst is 0.01-0.2mol/L, and obtaining a metal salt solution;
respectively cleaning the growth substrate with distilled water and ethanol, drying in vacuum, putting the dried growth substrate in a metal salt solution, soaking for 30min-2h at 20 ℃ under vacuum, and then drying the soaked growth substrate at 60-80 ℃ under vacuum;
fourthly, the growth substrate processed in the third step is placed above the silicon resin in the crucible, the crucible is placed in a vacuum high-temperature furnace, under the conditions that the heating rate is 1-10 ℃/min and the argon protection is carried out, the temperature is raised to 1300-1700 ℃, the temperature is kept for 1-5h, the temperature is lowered, the temperature lowering rate is set to be two hours and is lowered to 1000 ℃, and then the silicon carbide nanowire is obtained after natural cooling to the room temperature.
The second embodiment is as follows: the difference between the first embodiment and the second embodiment is that in the first embodiment, the silicone resin is polymethylsilsesquioxane, methylphenylsilicone, methylsilicone, low-phenyl methylsilicone, self-drying silicone, high-temperature silicone, epoxy-modified silicone, silicone polyester-modified resin, self-drying environmental silicone, non-stick coating MQ silicone, high-gloss silicone, benzyl transparent silicone, methyl transparent silicone, mica-bonded silicone, polymethylsilicone, amino silicone, fluorosilicone, silicone-epoxy, silicone polyester, solvent-resistant silicone, silicone adhesive, high-temperature-resistant methylsilicone, methyl MQ silicone or vinyl MQ silicone. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between the first and second embodiments is that the metal catalyst in the first step is Fe (CO)5、Fe2(CO)9、Fe(C5H5)、Fe3O4、FeCl2、FeCl2·6H2O、FeCl3、FeCl3·6H2O、Fe(NO)2、Fe(NO)3、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO)4、Ni(NO3)2、CuCl2、Cu(NO3)2、C22H14CuO4、Cu2O、Mn(NO3)2、(C17H35COO)2Mn、PdCl2、Y2O3、DyCl3、CoC2O4、CoCO3、CoO、CoCl2、Co(OH)2、Co(NH3)6、Co(CN)6、Co(SCN)4、Co(CO)4、Co(NO3)2. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: this embodiment is different from one of the first to third embodiments in that the crucible in the first step is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible, or a silicon carbide crucible; step three, the growth substrate is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the fourth embodiment and the first to the fourth embodiment is that the crucible is placed in a vacuum high temperature furnace, the temperature is raised under the condition that the flow rate of argon gas is 0.2ml/min, wherein the temperature raising rate is 3 ℃/min before reaching 600 ℃, the temperature is raised to 1400 ℃ at 5 ℃/min after reaching 600 ℃, then the temperature is raised to 1550 ℃ at the temperature raising rate of 1 ℃/min, the temperature is kept at 1550 ℃ for 3h, then the temperature is lowered, the temperature lowering rate is set to be two hours and is lowered to 1000 ℃, and then the crucible is naturally cooled to the room temperature. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the synthesis method of the silicon carbide nanowire according to the embodiment is carried out according to the following steps:
weighing silicon resin and a metal catalyst, mixing to obtain a mixture, wherein the mass fraction of the metal catalyst in the mixture is 1-10%, and putting the mixture into a crucible;
and secondly, respectively cleaning the growth substrate by using distilled water and ethanol, drying the growth substrate in vacuum at the temperature of 20-60 ℃, placing the dried growth substrate on the mixture in the crucible, then placing the crucible in a vacuum high-temperature furnace, heating the crucible to 1300-1700 ℃ under the conditions of heating rate of 1-10 ℃/min and argon protection, preserving the temperature for 1-5h, cooling the crucible, setting the cooling rate for two hours, cooling the temperature to 1000 ℃, and naturally cooling the crucible to room temperature to obtain the silicon carbide nanowire.
The seventh embodiment: the sixth difference between the present embodiment and the sixth embodiment is that the silicone resin in the first step is polymethylsilsesquioxane, methylphenylsilicone resin, methylsilicone resin, low-phenyl methylsilicone resin, self-drying silicone resin, high-temperature silicone resin, epoxy modified silicone resin, silicone polyester modified resin, self-drying environment-friendly silicone resin, non-stick coating MQ material silicone resin, highlight silicone resin, benzyl transparent silicone resin, methyl transparent silicone resin, mica bonded silicone resin, polymethylsilicone resin, amino silicone resin, fluorosilicone resin, silicone-epoxy resin, silicone polyester resin, solvent-resistant silicone resin, silicone resin adhesive, high-temperature resistant methylsilicone resin, methyl MQ silicone resin or vinyl MQ silicone resin; step one, the metal catalyst is Fe (CO)5、Fe2(CO)9、Fe(C5H5)、Fe3O4、FeCl2、FeCl2·6H2O、FeCl3、FeCl3·6H2O、Fe(NO)2、Fe(NO)3、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO)4、Ni(NO3)2、CuCl2、Cu(NO3)2、C22H14CuO4、Cu2O、Mn(NO3)2、(C17H35COO)2Mn、PdCl2、Y2O3、DyCl3、CoC2O4、CoCO3、CoO、CoCl2、Co(OH)2、Co(NH3)6、Co(CN)6、Co(SCN)4、Co(CO)4、Co(NO3)2(ii) a Step one, the crucible is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible or a silicon carbide crucible; the growth substrate in the second step is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the difference between the sixth embodiment and the seventh embodiment is that in the second step, the crucible is placed in a vacuum high-temperature furnace, the temperature is raised under the condition that the flow rate of argon gas is 0.2ml/min, wherein the temperature raising rate is 3 ℃/min before reaching 600 ℃, the temperature is raised to 1000 ℃ at 5 ℃/min after reaching 600 ℃, the temperature is kept at 1000 ℃ for 15min, then the temperature is raised to 1650 ℃ at the temperature raising rate of 3 ℃/min, the temperature is kept at 1650 ℃ for 3h, then the temperature is reduced, the temperature is reduced to 1000 ℃ after the temperature reduction rate is set for two hours, and then the crucible is naturally cooled to room temperature. The rest is the same as the sixth or seventh embodiment.
The specific implementation method nine: the difference between the sixth embodiment and the eighth embodiment is that in the second step, the crucible is placed in a vacuum high-temperature furnace, the temperature is raised under the condition that the flow rate of argon gas is 0.2ml/min, wherein the temperature raising rate is 3 ℃/min before the temperature reaches 600 ℃, the temperature is raised to 1400 ℃ at 5 ℃/min after the temperature reaches 600 ℃, the temperature is kept at 1400 ℃ for 15min, then the temperature is raised to 1500 ℃ at the temperature raising rate of 3 ℃/min, the temperature is kept at 1500 ℃ for 3h, then the temperature is reduced, the temperature reduction rate is set to be two hours, the temperature is reduced to 1000 ℃, and then the temperature is naturally cooled to the room temperature. The others are the same as the sixth to eighth embodiments.
The detailed implementation mode is ten: the difference between the sixth embodiment and the ninth embodiment is that in the second step, the crucible is placed in a vacuum high-temperature furnace, the temperature is raised under the condition that the flow rate of argon gas is 0.2ml/min, wherein the temperature raising rate is 3 ℃/min before the temperature reaches 600 ℃, the temperature is raised to 1400 ℃ at 5 ℃/min after the temperature reaches 600 ℃, the temperature is kept for 180min at 1400 ℃, then the temperature is reduced, the temperature reduction rate is set to be reduced to 1000 ℃ for two hours, and then the crucible is naturally cooled to the room temperature. The rest is the same as the sixth to ninth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
the synthesis method of the silicon carbide nanowire comprises the following steps:
one, choose (C)2H5)2Ni is used as a metal catalyst, 3g of polymethylsilsesquioxane resin powder is weighed, and the catalyst and the resin powder are uniformly mixed to obtain a mixed material, wherein the mass fraction of the catalyst is 6%;
secondly, respectively cleaning carbon cloth by using distilled water and ethanol, placing the cleaned carbon cloth in a vacuum drying oven at 30 ℃ for drying for 30min, placing the mixed material into a corundum crucible, placing the dried carbon cloth above the mixed material, placing the corundum crucible into a vacuum high-temperature furnace, replacing and vacuumizing with argon (repeating for three times), adjusting the flow rate of the argon to be 0.2ml/min, setting a temperature-raising program, raising the temperature to be 3 ℃/min before 600 ℃, then raising the temperature to 1000 ℃ at 5 ℃/min, preserving the temperature for 15min at 1000 ℃, then raising the temperature to 1650 ℃ at 3 ℃/min, preserving the temperature for 3h at 1650 ℃, then lowering the temperature to 1000 ℃ for two hours, then naturally cooling to room temperature, growing a large amount of grey green hairs on the carbon cloth, analyzing the grey green hairs as 3℃ -SiC through XRD, analyzing by SEM, and controlling the diameter to be 50-200 nm.
Experiment two:
the synthesis method of the silicon carbide nanowire comprises the following steps:
firstly, selecting FeCl3·6H2Taking O as a catalyst, weighing 4g of low phenyl methyl silicone resin powder, and adding FeCl into a mortar3·6H2Grinding for 15min, adding the ground catalyst and resin powder into a closed container, uniformly mixing the catalyst and the resin powder in a vibration mode to obtain a mixture, wherein the mass fraction of the catalyst is 6.5%, and then transferring the mixture into a graphite ark;
and secondly, respectively cleaning the graphite felt by using distilled water and ethanol, drying the cleaned graphite felt in a vacuum drying oven at the temperature of 60 ℃, putting the dried graphite felt above the mixed material, and covering a graphite boat cover above the mixed material. Placing the graphite boat into a tube furnace for high-temperature treatment, replacing and vacuumizing by argon (repeating for three times), adjusting the flow rate of the argon gas to be 0.2ml/min, setting a heating program, wherein the heating rate is 3 ℃/min before 600 ℃, then heating to 1400 ℃ at 5 ℃/min, maintaining at 1400 ℃ for 15min, then heating to 1500 ℃ at the heating rate of 3 ℃/min, preserving the heat at 1500 ℃ for 3h, then starting to cool, setting the cooling rate to be two hours, reducing to 1000 ℃, and then naturally cooling to room temperature. A large number of SiC nanowires are grown on the graphite felt and graphite ark, and a large number of SiC particles are produced in the crucible.
The SiC particles and the SiC nanowires are analyzed to be 3C-SiC by XRD, and the diameter of the SiC nanowires is 10-100nm and the diameter of the SiC particles is about 500nm by SEM analysis.
Experiment three:
the synthesis method of the silicon carbide nanowire comprises the following steps:
one, choose (C)2H5)2Ni as catalyst, polymethyl silicone resin powder and (C)2H5)2Uniformly mixing Ni to obtain a mixture, wherein the mass fraction of the catalyst is 5%, putting the mixture into a molybdenum crucible, and covering a mullite sheet above the crucible;
secondly, the molybdenum crucible is placed into a vacuum high-temperature furnace for heating treatment, argon is used for replacement and vacuumizing (repeated for three times), the flow rate of the argon is adjusted to be 0.2ml/min, a temperature rising program is set, the temperature rising rate is 3 ℃/min before 600 ℃, then the temperature rises to 1400 ℃ at 5 ℃/min, the temperature is maintained at 1400 ℃ for 180min, the temperature lowering rate is set to be two hours and is reduced to 1000 ℃, and then the molybdenum crucible is naturally cooled to the room temperature. A large number of white wool silicon carbide nanowires with the diameter of 20-50nm are grown on the mullite wafer, and a large number of SiC particles with uniform diameter are generated in the crucible, wherein the diameter of the SiC particles is about 1 um.
Experiment four:
the synthesis method of the silicon carbide nanowire comprises the following steps:
selecting FeCl3Is used as a catalyst and is added with a catalyst,ethanol is used as a solvent to prepare FeCl with the concentration of 0.06mol/L3A solution;
secondly, using the graphite felt as a growth substrate, respectively cleaning the graphite felt by using distilled water and ethanol, then placing the graphite felt in a vacuum drying oven at 60 ℃ for drying treatment, and placing the dried graphite felt in FeCl3The solution is soaked for 2 hours under the vacuum condition of 20 ℃, and then the soaked graphite felt is placed in a vacuum drying oven at 60 ℃ to be dried for 1 hour.
Weighing 3g of organic silicon-epoxy silicon resin powder, placing the organic silicon-epoxy silicon resin powder in an alumina crucible, and placing the treated graphite felt above the resin powder. And placing the alumina crucible in a vacuum drying furnace for high-temperature treatment. Replacing and vacuumizing with argon (repeating for three times), adjusting the flow rate of the argon to be 0.2ml/min, setting a temperature-raising program, wherein the temperature-raising rate is 3 ℃/min before 600 ℃, then raising the temperature to 1400 ℃ at 5 ℃/min, then raising the temperature to 1550 ℃ at the temperature-raising rate of 1 ℃/min, preserving the temperature for 3h at 1550 ℃, then beginning to lower the temperature, setting the temperature-lowering rate to be two hours, reducing the temperature to 1000 ℃, and then naturally cooling to the room temperature. A large number of white wool silicon carbide nanowires with the diameter of 20-50nm are grown on the graphite felt, and a large number of SiC particles with uniform diameter are generated in the crucible, and the diameter of the SiC particles is about 500 nm.
Claims (5)
1. The synthesis method of the silicon carbide nanowire is characterized by comprising the following steps of:
firstly, weighing silicon resin and a metal catalyst, and putting the silicon resin into a crucible;
dissolving a metal catalyst by using absolute ethyl alcohol, wherein the concentration of the catalyst is 0.01-0.2mol/L, and obtaining a metal salt solution;
respectively cleaning the growth substrate with distilled water and ethanol, drying in vacuum, putting the dried growth substrate in a metal salt solution, soaking for 30min-2h at 20 ℃ under vacuum, and then drying the soaked growth substrate at 60-80 ℃ under vacuum;
fourthly, placing the growth substrate processed in the third step above the silicon resin in the crucible, placing the crucible in a vacuum high-temperature furnace, heating up under the condition that the flow rate of argon is 0.2ml/min, wherein the heating rate is 3 ℃/min before the temperature reaches 600 ℃, heating up to 1400 ℃ at 5 ℃/min after the temperature reaches 600 ℃, then heating up to 1550 ℃ at the heating rate of 1 ℃/min, preserving the heat at 1550 ℃ for 3h, then starting to cool down, setting the cooling rate to be 1000 ℃ for two hours, and then naturally cooling to room temperature to obtain the silicon carbide nanowire;
step one, the silicon resin is polymethyl silsesquioxane, methyl phenyl silicon resin, methyl silicon resin, epoxy modified organic silicon resin, organic silicon polyester modified resin, non-stick coating MQ material organic silicon resin, benzyl transparent silicon resin, polymethyl silicon resin, organic silicon-epoxy resin, organic silicon polyester resin, methyl MQ silicon resin or vinyl MQ silicon resin.
2. The method for synthesizing silicon carbide nanowires of claim 1, wherein the metal catalyst in the first step is Fe (CO)5、Fe2(CO)9、Fe3O4、FeCl2、FeCl2▪6H2O、FeCl3、FeCl3▪6H2O、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO) 4Or Ni (NO)3)2。
3. The method for synthesizing silicon carbide nanowires according to claim 1, wherein the crucible of step one is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible, or a silicon carbide crucible;
step three, the growth substrate is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3。
4. The synthesis method of the silicon carbide nanowire is characterized by comprising the following steps of:
weighing silicon resin and a metal catalyst, mixing to obtain a mixture, wherein the mass fraction of the metal catalyst in the mixture is 1-10%, and putting the mixture into a crucible;
cleaning the growth substrate with distilled water and ethanol respectively, drying in vacuum at 20-60 ℃, placing the dried growth substrate on the mixture in a crucible, then placing the crucible in a vacuum high-temperature furnace, heating up under the condition that the argon flow rate is 0.2ml/min, wherein the heating rate is 3 ℃/min before reaching 600 ℃, the temperature is increased to 1000 ℃ at 5 ℃/min after reaching 600 ℃, keeping at 1000 ℃ for 15min, then increasing to 1650 ℃ at the heating rate of 3 ℃/min, keeping at 1650 ℃ for 3h, then starting to cool, setting the cooling rate for two hours, reducing to 1000 ℃, and then naturally cooling to room temperature to obtain the silicon carbide nanowire;
step one, the silicon resin is polymethyl silsesquioxane, methyl phenyl silicon resin, methyl silicon resin, epoxy modified organic silicon resin, organic silicon polyester modified resin, non-stick coating MQ material organic silicon resin, benzyl transparent silicon resin, polymethyl silicon resin, organic silicon-epoxy resin, organic silicon polyester resin, methyl MQ silicon resin or vinyl MQ silicon resin;
or in the second step, the crucible is placed in a vacuum high-temperature furnace, the temperature is raised under the condition that the flow rate of argon gas is 0.2ml/min, wherein the heating rate is 3 ℃/min before the temperature reaches 600 ℃, the temperature is raised to 1400 ℃ at 5 ℃/min after the temperature reaches 600 ℃, the temperature is kept at 1400 ℃ for 15min, then the temperature is raised to 1500 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 3h at 1500 ℃, then the temperature is reduced, the temperature is reduced to 1000 ℃ after the temperature is reduced for two hours, and the crucible is naturally cooled to the room temperature;
or in the second step, the crucible is placed in a vacuum high-temperature furnace, the temperature is raised under the condition that the flow rate of argon is 0.2ml/min, wherein the temperature raising rate is 3 ℃/min before the temperature reaches 600 ℃, the temperature is raised to 1400 ℃ at 5 ℃/min after the temperature reaches 600 ℃, the temperature is kept for 180min at 1400 ℃, then the temperature is lowered, the temperature lowering rate is set to be two hours, the temperature is lowered to 1000 ℃, and the crucible is naturally cooled to the room temperature.
5. Silicon carbide according to claim 4The synthesis method of the nano wire is characterized in that the metal catalyst in the step one is Fe (CO)5、Fe2(CO)9、Fe3O4、FeCl2、FeCl2▪6H2O、FeCl3、FeCl3▪6H2O、Fe2O3、NiCl2、NiBr2、NiI2、NiO、Ni(OH)2、(C2H5)2Ni、Ni(CO) 4Or Ni (NO)3)2；
Step one, the crucible is a corundum crucible, a graphite crucible, a quartz crucible, a platinum crucible, an alumina crucible, a platinum crucible, a molybdenum crucible or a silicon carbide crucible;
the growth substrate in the second step is graphite felt, carbon fiber, carbon cloth, SiC fiber cloth, SiC single crystal wafer, graphite sheet and SiO2Fibers, alumina silicate fibers, glass fibers, mullite sheets, alumina fibers, zirconia fibers, polyimide fibers, aramid fibers, Si nanowires, or Al2O3。
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| Title |
|---|
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| Synthesis and growth of SiC/SiO2 nanocables decorated with laminated porous ceramics from filter paper and polymeric precursor;Pan, JM et al;《CERAMICS INTERNATIONAL》;20130129;全文 * |
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