CN103387220B - Method for preparing sustainable high-yield carbon microtubes - Google Patents
Method for preparing sustainable high-yield carbon microtubes Download PDFInfo
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- CN103387220B CN103387220B CN201310313648.XA CN201310313648A CN103387220B CN 103387220 B CN103387220 B CN 103387220B CN 201310313648 A CN201310313648 A CN 201310313648A CN 103387220 B CN103387220 B CN 103387220B
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Abstract
The invention discloses a method for preparing sustainable high-yield carbon microtubes, relating to a method for preparing sustainable high-yield carbon microtubes. The invention aims to solve the problem that the yield of carbon microtubes prepared by the existing methods is low. The method disclosed by the invention comprises the following steps of: 1, placing a graphite crucible filled with a mixture of ethylene glycol and urea into a gas pressure sintering furnace, and vacuumizing; 2, feeding high-purity nitrogen or argon gas into the gas pressure sintering furnace; 3, when the temperature of the gas pressure sintering furnace raises to 900-1500 DEG C, carrying out heat preservation for 30-120 min; and 4, feeding a gas mixture of methane and ammonia gas into the gas pressure sintering furnace, carrying out heat preservation, and cooling the gas pressure sintering furnace to room temperature, thereby obtaining a microtube. According to the invention, the continuous operation of a reaction for microtube preparation can be ensured through the continuous addition of raw materials, and the yield of the prepared microtubes is high. The method disclosed by the invention is applied to the preparation of carbon microtubes.
Description
Technical field
The present invention relates to the preparation method of sustainable high yield carbon micron tube.
Background technology
In modern war, the development of stealthy technique is the important means that improves prominent anti-, the overall fighting efficiency of weaponry existence.Micron, nano-carbon material become the wave absorbing agent solid support material of the tool potentiality to be exploited of a new generation.Carbon micron tube is as electrical loss type wave absorbing agent, the advantage that has a lot of other materials not compare, as: proportion is little, mechanics that chemical stability is good, unique, electricity, magnetic performance etc.Due to the caliber of its micron dimension, also overcome the deficiency of carbon nanotube at aspects such as micro-nano fluid, micro-nano reaction vessels, and more easily realized single operation in addition.And be different from the carbon nanotube by graphite flake layer cans, and carbon micron tube is a kind of carbon pipe forming that overlapped by multiple graphite flake layers, other characteristics that this has also given it and differ from nanotube become the research object of recent many Chinese scholars.The preparation of carbon micron tube at present mainly contains template, catalysis method and chemical vapor deposition (CVD) method.Existing method is main raw material by urea, adopt CVD method successfully to prepare carbon micron tube, but output is relatively low, therefore needs to explore the novel process of the high-purity carbon micron tube of a kind of sustainable a large amount of productions.
Summary of the invention
The object of the invention is the problem yielding poorly in order to solve carbon micron tube that existing method prepares, a kind of preparation method of sustainable high yield carbon micron tube is provided.
The preparation method of the sustainable high yield carbon micron tube of the present invention, realizes by following steps:
One, be that the ratio of 0.5～10:100 mixes in mass ratio by ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, then the plumbago crucible that solid mixture is housed being placed in gas pressure sintering stove, will be 0.1Pa～1Pa to gas pressure sintering stove evacuation to pressure in stove after gas pressure sintering furnace body sealing;
Two, in the gas pressure sintering stove after vacuumizing to step 1, be filled with high pure nitrogen or argon gas, make pressure in gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 DEG C/min～30 DEG C/min at gas pressure sintering stove temperature rise rate, gas pressure sintering furnace temperature risen to after 900 DEG C～1500 DEG C, insulation 30min～120min;
Four, after step 3 insulation finishes, in adjustable pressure sintering oven, pressure is to 0.5MPa～4MPa, again to the mixed gas that passes into methane or methane and ammonia in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1MPa～2MPa, at 900 DEG C～1500 DEG C temperature, continue after insulation 30min～120min, be cooled to room temperature, obtain carbon micron tube; Wherein in the mixed gas of the methane described in step 4 and ammonia, the volumn concentration of methane is 1%～10%, and the volumn concentration of ammonia is 90%～99%.
Beneficial effect of the present invention:
1, to prepare carbon micron tube be that raw material is cheap taking urea and ethylene glycol as raw material to the method, and cost is low;
2, to prepare the technique of carbon micron tube simple for the method;
3, the temperature of reaction of the method is only 900 DEG C～1500 DEG C, and does not use catalyzer, there is no the impurity such as carbon granule, and carbon micron tube purity prepared by the method is high;
4, the carbon atmosphere that the method provides carbon micron tube to grow required by supplementing the mixed gas of methane or methane and ammonia, prepared carbon micron tube diameter is about 1.1 μ m, it is every stove 2.5g～10g that the method is prepared carbon micron tube output high, it is every stove 1g～2g that existing method is prepared carbon micron tube output, and result shows that this preparation method has improved the output of carbon micron tube;
5, the method can by raw material continue to add ensure to prepare carbon micron tube reaction continue carry out.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the carbon micron tube of preparation in embodiment mono-;
Fig. 2 is the scanning electron microscope (SEM) photograph of 1500 times of the carbon micron tubes of preparation in embodiment mono-;
Fig. 3 is the scanning electron microscope (SEM) photograph of 5000 times of the carbon micron tubes of preparation in embodiment mono-;
Fig. 4 is macroscopical output shape appearance figure of the carbon micron tube of preparation in embodiment mono-.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of the sustainable high yield carbon micron tube of present embodiment, carries out according to the following steps:
One, be that the ratio of 0.5～10:100 mixes in mass ratio by ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, then the plumbago crucible that solid mixture is housed being placed in gas pressure sintering stove, will be 0.1Pa～1Pa to gas pressure sintering stove evacuation to pressure in stove after gas pressure sintering furnace body sealing;
Two, in the gas pressure sintering stove after vacuumizing to step 1, be filled with high pure nitrogen or argon gas, make pressure in gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 DEG C/min～30 DEG C/min at gas pressure sintering stove temperature rise rate, gas pressure sintering furnace temperature risen to after 900 DEG C～1500 DEG C, insulation 30min～120min;
Four, after step 3 insulation finishes, in adjustable pressure sintering oven, pressure is to 0.5MPa～4MPa, again to the mixed gas that passes into methane or methane and ammonia in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1MPa～2MPa, at 900 DEG C～1500 DEG C temperature, continue after insulation 30min～120min, be cooled to room temperature, obtain carbon micron tube; Wherein in the mixed gas of the methane described in step 4 and ammonia, the volumn concentration of methane is 1%～10%, and the volumn concentration of ammonia is 90%～99%.
The beneficial effect of present embodiment:
1, to prepare carbon micron tube be that raw material is cheap taking urea and ethylene glycol as raw material to the method, and cost is low;
2, to prepare the technique of carbon micron tube simple for the method;
3, the temperature of reaction of the method is only 900 DEG C～1500 DEG C, and does not use catalyzer, there is no the impurity such as carbon granule, and carbon micron tube purity prepared by the method is high;
4, the carbon atmosphere that the method provides carbon micron tube to grow required by supplementing the mixed gas of methane or methane and ammonia, prepared carbon micron tube diameter is about 1.1 μ m, it is every stove 2.5g～10g that the method is prepared carbon micron tube output high, it is every stove 1g～2g that existing method is prepared carbon micron tube output, and result shows that this preparation method has improved the output of carbon micron tube;
5, the method can by raw material continue to add ensure to prepare carbon micron tube reaction continue carry out.
Embodiment two: present embodiment is different from embodiment one: in step 1, ethylene glycol and urea are in mass ratio for the ratio of 0.5:100 mixes.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the pressure described in step 1 is 0.2Pa～0.9Pa.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: in the gas pressure sintering stove described in step 2, pressure is 0.8MPa.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the temperature rise rate described in step 3 is 10 DEG C/min.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the gas pressure sintering furnace temperature described in step 3 rises to after 1100 DEG C～1300 DEG C, insulation 60min～90min.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: in the adjustable pressure sintering oven described in step 4, pressure is to 1MPa～1.5MPa.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: described in step 4 again to the mixed gas that passes into methane or methane and ammonia in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1.7MPa.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: described in step 4 1300 DEG C continue insulation 60min.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: quality percentage composition >=99.999% of high pure nitrogen in step 2; Quality percentage composition >=99.999% of argon gas.Other is identical with one of embodiment one to nine.
Embodiment mono-:
The preparation method of the sustainable high yield carbon micron tube of present embodiment, realizes by following steps:
One, by ethylene glycol and urea in mass ratio for the ratio of 0.5:100 mixes, obtain solid mixture, solid mixture is put into plumbago crucible, then the plumbago crucible that solid mixture is housed being placed in gas pressure sintering stove, will be 0.1Pa to gas pressure sintering stove evacuation to pressure in stove after gas pressure sintering furnace body sealing;
Two, in the gas pressure sintering stove after vacuumizing to step 1, be filled with high pure nitrogen, make pressure in gas pressure sintering stove reach 0.8MPa;
Three, be under the condition of 10 DEG C/min at gas pressure sintering stove temperature rise rate, gas pressure sintering furnace temperature is risen to after 1300 DEG C, insulation 90min;
Four,, after step 3 insulation finishes, in adjustable pressure sintering oven, pressure, to 1.5MPa, then passes into methane in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1.7MPa, at 1300 DEG C of temperature, continue, after insulation 60min, to be cooled to room temperature, obtain carbon micron tube; Wherein the quality percentage composition of the high pure nitrogen described in step 2 is 99.999%.
Carbon micron tube prepared by the present embodiment carries out thing with X-ray diffractometer and detects mutually, and as shown in Figure 1, result shows that the carbon micron tube of preparation is without other impurity to X-ray diffractogram.
Carbon micron tube prepared by the present embodiment is observed microscopic appearance by scanning electronic microscope, the scanning electron microscope (SEM) photograph of 1500 times as shown in Figure 2, as shown in Figure 3, the pattern of the carbon micron tube of preparation is the carbon pipe that the curling overlap joint of graphite flake layer forms to the scanning electron microscope (SEM) photograph of 5000 times, and diameter is about 1.1 μ m.
The output of carbon micron tube prepared by the present embodiment is every stove 8.5g.
As shown in Figure 4, the carbon micron tube output of preparation is high as shown in Figure 4 for macroscopical output shape appearance figure of the carbon micron tube obtaining by the preparation method of the sustainable high yield carbon micron tube of the present embodiment.
Embodiment bis-:
The preparation method of the sustainable high yield carbon micron tube of present embodiment, realizes by following steps:
One, by ethylene glycol and urea in mass ratio for the ratio of 0.5:100 mixes, obtain solid mixture, solid mixture is put into plumbago crucible, then the plumbago crucible that solid mixture is housed being placed in gas pressure sintering stove, will be 0.1Pa to gas pressure sintering stove evacuation to pressure in stove after gas pressure sintering furnace body sealing;
Two, in the gas pressure sintering stove after vacuumizing to step 1, be filled with high pure nitrogen, make pressure in gas pressure sintering stove reach 0.8MPa;
Three, be under the condition of 10 DEG C/min at gas pressure sintering stove temperature rise rate, gas pressure sintering furnace temperature is risen to after 1300 DEG C, insulation 90min;
Four,, after step 3 insulation finishes, in adjustable pressure sintering oven, pressure is to 1.5MPa, then to the mixed gas that passes into methane and ammonia in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1.7MPa, at 1300 DEG C of temperature, continue, after insulation 60min, to be cooled to room temperature, obtain carbon micron tube; Wherein in the mixed gas of the methane described in step 4 and ammonia, the volumn concentration of methane is 5%, and the volumn concentration of ammonia is 95%; Wherein the quality percentage composition of the high pure nitrogen described in step 2 is 99.999%.
The output of carbon micron tube prepared by the present embodiment is every stove 4.5g.
Claims (8)
1. a preparation method for sustainable high yield carbon micron tube, is characterized in that comprising the following steps:
One, be that the ratio of 0.5～10:100 mixes in mass ratio by ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, then the plumbago crucible that solid mixture is housed being placed in gas pressure sintering stove, will be 0.1Pa～1Pa to gas pressure sintering stove evacuation to pressure in stove after gas pressure sintering furnace body sealing;
Two, in the gas pressure sintering stove after vacuumizing to step 1, be filled with high pure nitrogen or argon gas, make pressure in gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 DEG C/min～30 DEG C/min at gas pressure sintering stove temperature rise rate, gas pressure sintering furnace temperature risen to after 900 DEG C～1500 DEG C, insulation 30min～120min;
Four, after step 3 insulation finishes, in adjustable pressure sintering oven, pressure is to 1MPa～1.5MPa, again to the mixed gas that passes into methane or methane and ammonia in gas pressure sintering stove, make pressure in gas pressure sintering stove reach 1.7MPa, at 900 DEG C～1500 DEG C temperature, continue after insulation 30min～120min, be cooled to room temperature, obtain carbon micron tube; Wherein in the mixed gas of the methane described in step 4 and ammonia, the volumn concentration of methane is 1%～10%, and the volumn concentration of ammonia is 90%～99%.
2. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 1, is characterized in that in step 1 that ethylene glycol and urea are in mass ratio for the ratio of 0.5:100 mixes.
3. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 1, is characterized in that the pressure described in step 1 is 0.2Pa～0.9Pa.
4. according to the preparation method of a kind of sustainable high yield carbon micron tube described in claim 1,2 or 3, it is characterized in that in the gas pressure sintering stove described in step 2, pressure is 0.8MPa.
5. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 4, is characterized in that the temperature rise rate described in step 3 is 10 DEG C/min.
6. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 5, is characterized in that the gas pressure sintering furnace temperature described in step 3 rises to after 1100 DEG C～1300 DEG C, insulation 60min～90min.
7. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 6, it is characterized in that described in step 4 1300 DEG C continue insulation 60min.
8. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 7, is characterized in that quality percentage composition >=99.999% of the high pure nitrogen described in step 2; Quality percentage composition >=99.999% of argon gas.
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| CN109941984B (en) * | 2019-05-09 | 2020-08-04 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon micro-tube and carbon micro-tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597503A (en) * | 2004-09-16 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Carbon micron pipe formed by nanometer carbon particles and its preparation method |
| CN101817971A (en) * | 2010-05-27 | 2010-09-01 | 哈尔滨工业大学 | Carbon micro-tube epoxy resin wave-absorbing composite material and preparation method thereof |
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| JP2005239439A (en) * | 2004-02-24 | 2005-09-08 | National Institute For Materials Science | Method of manufacturing carbon microtube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597503A (en) * | 2004-09-16 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Carbon micron pipe formed by nanometer carbon particles and its preparation method |
| CN101817971A (en) * | 2010-05-27 | 2010-09-01 | 哈尔滨工业大学 | Carbon micro-tube epoxy resin wave-absorbing composite material and preparation method thereof |
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| JP特开2005-239439A 2005.09.08 * |
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