CN104386698A - Fluidized bed chemical vapor deposition preparation method of silicon carbide nanowire - Google Patents
Fluidized bed chemical vapor deposition preparation method of silicon carbide nanowire Download PDFInfo
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- CN104386698A CN104386698A CN201410636382.7A CN201410636382A CN104386698A CN 104386698 A CN104386698 A CN 104386698A CN 201410636382 A CN201410636382 A CN 201410636382A CN 104386698 A CN104386698 A CN 104386698A
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Abstract
The invention provides a fluidized bed chemical vapor deposition preparation method of a silicon carbide nanowire, which comprises the following steps: controlling the heating mode of a fluidized pipe to sequentially form an upper low-temperature region, a middle high-temperature region and a lower low-temperature region sequentially from top to bottom in the vertical direction; fluidizing catalyst particles in the lower low-temperature region and the middle high-temperature region under the action of fluidized gas, and forming catalyst nano liquid drops in the middle high-temperature region; introducing precursor raw material steam for preparation of silicon carbide into the middle high-temperature region through carrying gas to be subjected to pyrolysis and be combined with the catalyst nano liquid drops to generate crystal nuclei; and feeding the crystal nuclei to the upper low-temperature region of the fluidized pipe through the gas flow, growing, and crystallizing to form the silicon carbide nanowire. The preparation method provided by the invention is simple in technical process, convenient in technological operation and low in cost; the catalyst is in the form of solid particles, so that the catalyst can be filled in large quantities and supplemented subsequently; and the silicon carbide nanowire product can be sucked out through negative pressure in the production process, thus realizing continuous production.
Description
Technical field
The present invention relates to one dimension carbofrax material preparing technical field, specifically, relate to a kind of fluidized-bed chemical vapor deposition preparation method of silicon carbide nanometer line.
Background technology
Have the monodimension nanometer material of very big length-to-diameter ratio, size anisotropy makes it show novel physics chemical property not available for block materials.In the monodimension nanometer material of numerous kinds, silicon carbide nanometer line is because of in electron transport, and photochemical catalysis, super-hydrophobic, the excellent properties in the fields such as superplasticity, makes it in structure nano functional device, have potential broad prospect of application.Simultaneously due to the mechanical property of silicon carbide excellence, antioxidant property, corrosion resistance nature, can at higher temperature, more high-power, is on active service under more harsh environment.
The method preparing silicon carbide nanometer line at present mainly contains: (1) by carbon pipe, carbon fiber or silicon nanowires conversion method; (2) chemical Vapor deposition process; (3) silicon-carbon oxide hot reducing method; (4) thermal evaporation etc.These methods reactor used is horizontal fixed-bed reactor, and reaction system is closed, and reactant need be put in advance, and preparation cycle is long, and product yield is low, and product purity is low, is not suitable for suitability for industrialized production.And the reactor of another kind of form, vertical fluidized bed bioreactor can realize continuous seepage in enormous quantities, is widely used at chemical field.At present, the method preparing silicon carbide nanometer line that fluid mapper process and chemical vapour deposition combined not relevant report.
Summary of the invention
In order to solve problems of the prior art, the object of this invention is to provide and a kind ofly suitability for industrialized production high purity can prepare the method for silicon carbide nanometer line.
In order to realize the object of the invention, the invention provides a kind of fluidized-bed chemical vapor deposition preparation method of silicon carbide nanometer line, described preparation method specifically comprises the steps:
1) by controlling the type of heating of fluidisation pipe, it is made to form cold zone, top, high-temperature zone, middle part and cold zone, bottom successively from top to bottom at vertical direction;
2) granules of catalyst carries out fluidisation in cold zone, bottom and high-temperature zone, middle part under fluidizing agent effect, and forms catalyst nano drop in high-temperature zone, middle part;
3) the precursor material steam preparing silicon carbide enters middle part high-temperature zone pyrolysis by carrier band gas, is combined produces nucleus with catalyst nano drop;
4) nucleus is brought to cold zone, fluidisation pipe top by air-flow, forms silicon carbide nanometer line through growth, crystallization.
Further, the temperature of high-temperature zone, described middle part is 1400 DEG C ~ 1600 DEG C, and the temperature of cold zone, bottom is 1200 DEG C ~ 1400 DEG C, and the temperature of cold zone, top is 1000 DEG C ~ 1400 DEG C.
Further, described granules of catalyst is the particle containing a kind of element simple substance in Fe, Co, Ni or its oxide compound.
Further, the particle diameter of described granules of catalyst is 200 μm ~ 900 μm.
Further, described precursor material steam is the steam that the mode of presoma employing electrically heated or water bath with thermostatic control produces, it is 25 DEG C ~ 60 DEG C that its temperature controls, and described precursor material is the one in METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS) and tri-methyl-chlorosilane.
Further, described fluidizing agent is Ar and H
2, the throughput ratio of two kinds of gases is Ar/H
2be 0 ~ 0.8; Described carrier band gas is H
2, the throughput ratio of carrier band gas and fluidizing agent is 0.01 ~ 0.05.
Further, the height ratio of cold zone, described top, high-temperature zone, middle part and cold zone, bottom is 3 ~ 5:1.5 ~ 2.5:0.75 ~ 1.
Further, the growth time of silicon carbide nanometer line is 1h ~ 4h.
Further, the silicon carbide nanometer line of formation can utilize negative pressure sucking-off from fluidisation pipe, can add raw catalyst particle continuously in reaction process.
Present invention also offers a kind of fluidized reaction equipment for the preparation of silicon carbide nanometer line, it is hollow tube, and body top has catalyzer feeding mouth, and upper portion side wall has pneumatic outlet, and its bottom has catalyzer discharge port and gas inlet; Body top is also provided with product discharge mouth, and is connected with the device that can form negative pressure; The blade diameter length ratio of described conversion unit is 1:6 ~ 1:12.
Beneficial effect of the present invention is:
The present invention is by reactor design structure, and after certain reaction times, silicon carbide nanometer line can utilize negative pressure sucking-off from the product discharge mouth of fluidisation pipe middle and upper part.After in reaction process, catalyzer exhausts, residual waste draws off by fluidisation pipe bottom discharge mouth, and adds raw catalyst particle continuously by top charging opening.
Present invention process flow process is simple, technological operation is convenient, cost is low, and catalyzer is solid particulate form, once can relatively largely put into, constantly separate out at high-temperature constant warm area, there is provided catalyzer endlessly, thus realize producing in enormous quantities, and the reinforced of catalyzer can be completed in reaction process, the sucking-off of discharging and silicon carbide nanometer line product, is conducive to realizing continuous prodution.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the vertical fluidized bed bioreactor used in preparation method of the present invention;
Fig. 2 is the XRD spectra of the embodiment of the present invention 1 gained silicon carbide nanometer line;
Fig. 3 is the stereoscan photograph of the embodiment of the present invention 1 gained silicon carbide nanometer line;
Fig. 4 is the transmission electron microscope photo of the embodiment of the present invention 1 gained silicon carbide nanometer line.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
The present invention adopts fluidized-bed chemical vapor deposition legal system for silicon carbide nanometer line, and as shown in Figure 1, concrete preparation process is as follows for vertical fluidized bed bioreactor schematic diagram:
1) by controlling the type of heating of fluidisation pipe, it is made from top to bottom to be divided into 1000 DEG C ~ 1400 DEG C, cold zone, top, 1400 DEG C ~ 1600 DEG C, high-temperature zone, middle part and 1200 DEG C ~ 1400 DEG C, cold zone, bottom at vertical direction; Fluidisation bore is 80mm, is highly 80cm.
2) granules of catalyst is in cold zone, bottom fluidisation under fluidizing agent effect, and under airflow function from bottom to top, enters the catalyst nano drop that high-temperature zone, middle part is formed;
Granules of catalyst is the particle containing Fe, Co, Ni simple substance or its oxide compound, and catalyst particle size is 200 μm ~ 900 μm;
Adopt a certain proportion of Ar and H
2for fluidizing agent, the throughput ratio scope Ar/H of two kinds of gases
2be 0 ~ 0.8.Adopt H
2for the carrier band gas of precursor vapor, the throughput ratio scope of carrier band gas and fluidizing agent is 0.01 ~ 0.05.
3) the precursor material steam preparing silicon carbide is entered middle part high-temperature zone pyrolysis by carrier band gas, be combined with catalyst nano drop and produce nucleus;
Presoma adopts the mode of electrically heated or water bath with thermostatic control to produce steam, and its temperature controlling range is 25 DEG C ~ 60 DEG C.
4) nucleus is brought to cold zone, fluidisation pipe top by air-flow from bottom to top, and crystallization also grows 1h ~ 4h, forms silicon carbide nanometer line, silicon carbide nanometer line is utilized negative pressure sucking-off from the product discharge mouth of fluidisation pipe middle and upper part.
5), after in reaction process, catalyzer exhausts, residual waste draws off by fluidisation pipe bottom discharge mouth, and adds raw catalyst particle continuously by top charging opening.
Embodiment 1
Adopt H
2for fluidizing agent, H
2flow be 6L/min, 40g ZrO
2-CoO (massfraction of CoO is 6%) particle is put into fluidized-bed and is carried out fluidisation 1300 DEG C time, and average diameter of particles is 600 μm.METHYL TRICHLORO SILANE constant temperature, at 35 DEG C, persistently overheatingly passes into METHYL TRICHLORO SILANE, H to 1500 DEG C
2for carrier band gas, carrier band airshed is 0.3L/min, and the reaction times is 1h.
By comparison standard card, the XRD spectra of reaction product as shown in Figure 2, can be found out that product is the silicon carbide of Emission in Cubic, there is no other dephasign.Silicon carbide nanometer line stereoscan photograph and transmission electron microscope photo are as shown in Fig. 3, Fig. 4, and can see the purity of nanowire higher (without nano particle or other forms of silicon carbide), nanowire length is at a hundreds of micrometer range, and diameter is 10 ~ 50nm.
Embodiment 2
Adopt H
2for fluidizing agent, H
2flow be that 3L/min, 20g metal Fe particle is put into fluidized-bed and carried out fluidisation 1300 DEG C time, average diameter of particles is 200 μm.METHYL TRICHLORO SILANE constant temperature, at 35 DEG C, persistently overheatingly passes into METHYL TRICHLORO SILANE, H to 1400 DEG C
2for carrier band gas, carrier band airshed is 0.15L/min, adds 20g metal Fe particle after reaction times 1h by fluidized-bed feeding mouth, continues reaction 1h.
Embodiment 3
Adopt Ar and H
2mixed gas be fluidizing agent, the flow of Ar is 0.85L/min, H
2flow be 6L/min, 40g ZrO
2-CoO (massfraction of CoO is 6%) particle is put into fluidized-bed and is carried out fluidisation 1300 DEG C time, and average diameter of particles is 800 μm.METHYL TRICHLORO SILANE constant temperature, at 35 DEG C, persistently overheatingly passes into METHYL TRICHLORO SILANE, H to 1580 DEG C
2for carrier band gas, carrier band airshed is 0.3L/min, and the reaction times is 1h.
Embodiment 4
Adopt H
2for fluidizing agent, H
2flow be 6L/min, 40g ZrO
2-CoO (massfraction of CoO is 6%) particle is put into fluidized-bed and is carried out fluidisation 1300 DEG C time, and average diameter of particles is 600 μm.Dimethyldichlorosilane(DMCS) constant temperature, at 40 DEG C, persistently overheatingly passes into dimethyldichlorosilane(DMCS), H to 1530 DEG C
2for carrier band gas, carrier band airshed is 0.3L/min, and the reaction times is 1h.
Embodiment 5
Adopt Ar and H
2mixed gas be fluidizing agent, the flow of Ar is 2.0L/min, H
2flow be that 18L/min, 60g WC-Co (massfraction of Co is 6%) particle is put into fluidized-bed and carried out fluidisation 1300 DEG C time, average diameter of particles is 900 μm.METHYL TRICHLORO SILANE constant temperature, at 30 DEG C, persistently overheatingly passes into METHYL TRICHLORO SILANE, H to 1600 DEG C
2for carrier band gas, carrier band airshed is 0.2L/min, and the reaction times is 4h.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a fluidized-bed chemical vapor deposition preparation method for silicon carbide nanometer line, is characterized in that, described preparation method specifically comprises the steps:
1) by controlling the type of heating of fluidisation pipe, it is made to form cold zone, top, high-temperature zone, middle part and cold zone, bottom successively from top to bottom at vertical direction;
2) granules of catalyst carries out fluidisation in cold zone, bottom and high-temperature zone, middle part under fluidizing agent effect, and forms catalyst nano drop in high-temperature zone, middle part;
3) the precursor material steam preparing silicon carbide enters middle part high-temperature zone pyrolysis by carrier band gas, is combined produces nucleus with catalyst nano drop;
4) nucleus is brought to cold zone, fluidisation pipe top by air-flow, forms silicon carbide nanometer line through growth, crystallization.
2. the preparation method of silicon carbide nanometer line according to claim 1, is characterized in that, the temperature of high-temperature zone, described middle part is 1400 DEG C ~ 1600 DEG C, and the temperature of cold zone, bottom is 1200 DEG C ~ 1400 DEG C, and the temperature of cold zone, top is 1000 DEG C ~ 1400 DEG C.
3. the preparation method of silicon carbide nanometer line according to claim 1 and 2, is characterized in that, described granules of catalyst is containing a kind of simple substance of element or the particle of its oxide compound in Fe, Co, Ni.
4. the preparation method of silicon carbide nanometer line according to claim 3, is characterized in that, the particle diameter of described granules of catalyst is 200 μm ~ 900 μm.
5. the preparation method of silicon carbide nanometer line according to claim 3, it is characterized in that, described precursor material steam is the steam that the mode of presoma employing electrically heated or water bath with thermostatic control produces, it is 25 DEG C ~ 60 DEG C that its temperature controls, and described precursor material is the one in METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS) and tri-methyl-chlorosilane.
6. the preparation method of silicon carbide nanometer line according to claim 3, is characterized in that, described fluidizing agent is Ar and H
2, the throughput ratio Ar/H of two kinds of gases
2be 0 ~ 0.8; Described carrier band gas is H
2, the throughput ratio of carrier band gas and fluidizing agent is 0.01 ~ 0.05.
7. the preparation method of silicon carbide nanometer line according to claim 3, is characterized in that, the height ratio of cold zone, described top, high-temperature zone, middle part and cold zone, bottom is 3 ~ 5:1.5 ~ 2.5:0.75 ~ 1.
8. the preparation method of silicon carbide nanometer line according to claim 3, is characterized in that, the growth time of silicon carbide nanometer line is 1h ~ 4h.
9. the preparation method of silicon carbide nanometer line according to claim 3, is characterized in that, the silicon carbide nanometer line of formation can utilize negative pressure sucking-off from fluidisation pipe, can add raw catalyst particle continuously in reaction process.
10. for the preparation of a fluidized reaction equipment for silicon carbide nanometer line, it is characterized in that, it is hollow tube, and body top has catalyzer feeding mouth, and upper portion side wall has pneumatic outlet, and its bottom has catalyzer discharge port and gas inlet; Body top is also provided with product discharge mouth, and is connected with the device that can form negative pressure; The blade diameter length ratio of described conversion unit is 1:6 ~ 1:12.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423635A (en) * | 2018-03-22 | 2018-08-21 | 清华大学 | A kind of three-dimensional spherical nanometer silicon carbide assembled material and its preparation method and application |
| CN111392730A (en) * | 2020-04-22 | 2020-07-10 | 扬州市汀月科技有限公司 | Method for preparing silicon carbide whisker by combining fluidized bed with carbothermic reduction reaction and application thereof |
| CN113564561A (en) * | 2020-04-29 | 2021-10-29 | 清华大学 | Powder particle coating equipment based on fluidized bed and chemical vapor deposition technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203474963U (en) * | 2013-07-04 | 2014-03-12 | 国家电网公司 | Chemical vapor deposition equipment for producing silicon carbide epitaxial wafer |
| CN104046959A (en) * | 2013-06-08 | 2014-09-17 | 唐治 | Chemical vapor deposition device for epitaxial growth of silicon carbide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046959A (en) * | 2013-06-08 | 2014-09-17 | 唐治 | Chemical vapor deposition device for epitaxial growth of silicon carbide |
| CN203474963U (en) * | 2013-07-04 | 2014-03-12 | 国家电网公司 | Chemical vapor deposition equipment for producing silicon carbide epitaxial wafer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423635A (en) * | 2018-03-22 | 2018-08-21 | 清华大学 | A kind of three-dimensional spherical nanometer silicon carbide assembled material and its preparation method and application |
| CN108423635B (en) * | 2018-03-22 | 2019-09-20 | 清华大学 | A kind of three-dimensional spherical nanometer silicon carbide assembled material and its preparation method and application |
| CN111392730A (en) * | 2020-04-22 | 2020-07-10 | 扬州市汀月科技有限公司 | Method for preparing silicon carbide whisker by combining fluidized bed with carbothermic reduction reaction and application thereof |
| CN111392730B (en) * | 2020-04-22 | 2022-08-30 | 扬州市汀月科技有限公司 | Method for preparing silicon carbide whisker by combining fluidized bed with carbothermic reduction reaction and application thereof |
| CN113564561A (en) * | 2020-04-29 | 2021-10-29 | 清华大学 | Powder particle coating equipment based on fluidized bed and chemical vapor deposition technology |
| CN113564561B (en) * | 2020-04-29 | 2022-05-06 | 清华大学 | Powder particle coating equipment based on fluidized bed and chemical vapor deposition technology |
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