CN103387220A - Method for preparing sustainable high-yield carbon microtubes - Google Patents
Method for preparing sustainable high-yield carbon microtubes Download PDFInfo
- Publication number
- CN103387220A CN103387220A CN201310313648XA CN201310313648A CN103387220A CN 103387220 A CN103387220 A CN 103387220A CN 201310313648X A CN201310313648X A CN 201310313648XA CN 201310313648 A CN201310313648 A CN 201310313648A CN 103387220 A CN103387220 A CN 103387220A
- Authority
- CN
- China
- Prior art keywords
- pressure sintering
- gas pressure
- preparation
- micron tube
- carbon micron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
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, the 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 carbon nanotube by the graphite flake layer cans, and carbon micron tube is a kind of carbon pipe that is formed by a plurality of graphite flake layers overlap joints, this has also given it and has differed from other characteristics of nanotube, becomes the research object of recent many Chinese scholars.The preparation of carbon current micron tube mainly contains template, catalysis method and chemical vapor deposition (CVD) method.Existing method is main raw material by urea, adopt the 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 objective of the invention is the problem that yields 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, realize by following steps:
One, be that the ratio of 0.5～10:100 mixes in mass ratio with ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, the plumbago crucible that then solid mixture will be housed is placed in the gas pressure sintering stove, will to gas pressure sintering stove evacuation to pressure in stove, be 0.1Pa～1Pa after gas pressure sintering furnace body sealing;
Two, be filled with high pure nitrogen or argon gas in the gas pressure sintering stove after vacuumizing to step 1, make pressure in the gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 ℃/min～30 ℃/min at gas pressure sintering stove temperature rise rate, after making the gas pressure sintering furnace temperature rise to 900 ℃～1500 ℃, insulation 30min～120min;
Four, after the step 3 insulation finishes, in the adjustable pressure sintering oven, pressure is to 0.5MPa～4MPa, again to the mixed gas that passes into methane or methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1MPa～2MPa, after continuing insulation 30min～120min at 900 ℃～1500 ℃ temperature, be cooled to room temperature, namely 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 take 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 ℃～1500 ℃, and does not use catalyzer, there is no the impurity such as carbon granule, and the carbon micron tube purity of the method preparation is high;
4, the method provides the carbon micron tube growth required carbon atmosphere by the mixed gas that supplements methane or methane and ammonia, prepared carbon micron tube diameter is about 1.1 μ m, the method prepares the high every stove 2.5g～10g of being of carbon micron tube output, it is every stove 1g～2g that existing method prepares 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 guarantee to prepare the carbon micron tube reaction continue carry out.
Description of drawings
Fig. 1 is the X-ray diffractogram of the carbon micron tube of preparation in embodiment one;
Fig. 2 is the scanning electron microscope (SEM) photograph of 1500 times of the carbon micron tubes of preparation in embodiment one;
Fig. 3 is the scanning electron microscope (SEM) photograph of 5000 times of the carbon micron tubes of preparation in embodiment one;
Fig. 4 is macroscopical output shape appearance figure of the carbon micron tube of preparation in embodiment one.
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, carry out according to the following steps:
One, be that the ratio of 0.5～10:100 mixes in mass ratio with ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, the plumbago crucible that then solid mixture will be housed is placed in the gas pressure sintering stove, will to gas pressure sintering stove evacuation to pressure in stove, be 0.1Pa～1Pa after gas pressure sintering furnace body sealing;
Two, be filled with high pure nitrogen or argon gas in the gas pressure sintering stove after vacuumizing to step 1, make pressure in the gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 ℃/min～30 ℃/min at gas pressure sintering stove temperature rise rate, after making the gas pressure sintering furnace temperature rise to 900 ℃～1500 ℃, insulation 30min～120min;
Four, after the step 3 insulation finishes, in the adjustable pressure sintering oven, pressure is to 0.5MPa～4MPa, again to the mixed gas that passes into methane or methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1MPa～2MPa, after continuing insulation 30min～120min at 900 ℃～1500 ℃ temperature, be cooled to room temperature, namely 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 take 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 ℃～1500 ℃, and does not use catalyzer, there is no the impurity such as carbon granule, and the carbon micron tube purity of the method preparation is high;
4, the method provides the carbon micron tube growth required carbon atmosphere by the mixed gas that supplements methane or methane and ammonia, prepared carbon micron tube diameter is about 1.1 μ m, the method prepares the high every stove 2.5g～10g of being of carbon micron tube output, it is every stove 1g～2g that existing method prepares 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 guarantee to prepare the carbon micron tube reaction continue carry out.
Embodiment two: what present embodiment was different from embodiment one is: in step 1, ethylene glycol and urea mix for the ratio of 0.5:100 in mass ratio.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: the pressure described in step 1 is 0.2Pa～0.9Pa.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: 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: what present embodiment was different from one of embodiment one to four is: the temperature rise rate described in step 3 is 10 ℃/min.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: after the gas pressure sintering furnace temperature described in step 3 rises to 1100 ℃～1300 ℃, and insulation 60min～90min.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: 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: what present embodiment was different from one of embodiment one to seven is: described in step 4 again to the mixed gas that passes into methane or methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1.7MPa.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is: continue insulation 60min at 1300 ℃ described in step 4.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is: the quality percentage composition of high pure nitrogen 〉=99.999% in step 2; The quality percentage composition of argon gas 〉=99.999%.Other is identical with one of embodiment one to nine.
Embodiment one:
The preparation method of the sustainable high yield carbon micron tube of present embodiment, realize by following steps:
One, ethylene glycol and urea are mixed for the ratio of 0.5:100 in mass ratio, obtain solid mixture, solid mixture is put into plumbago crucible, the plumbago crucible that then solid mixture will be housed is placed in the gas pressure sintering stove, will to gas pressure sintering stove evacuation to pressure in stove, be 0.1Pa after gas pressure sintering furnace body sealing;
Two, be filled with high pure nitrogen in the gas pressure sintering stove after vacuumizing to step 1, make pressure in the gas pressure sintering stove reach 0.8MPa;
Three, be under the condition of 10 ℃/min at gas pressure sintering stove temperature rise rate, after making the gas pressure sintering furnace temperature rise to 1300 ℃, insulation 90min;
Four, after step 3 insulation finishes, in the adjustable pressure sintering oven, pressure, to 1.5MPa, then passes into methane in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1.7MPa, after continuing insulation 60min at 1300 ℃ of temperature, be cooled to room temperature, namely obtain carbon micron tube; Wherein the quality percentage composition of the high pure nitrogen described in step 2 is 99.999%.
The carbon micron tube of the present embodiment preparation is carried out phase with X-ray diffractometer detect, as shown in Figure 1, result shows that the carbon micron tube of preparation is without other impurity to X-ray diffractogram.
The carbon micron tube of the present embodiment preparation is observed microscopic appearance with 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 the carbon micron tube of the present embodiment preparation 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 that the preparation method by the sustainable high yield carbon micron tube of the present embodiment obtains.
Embodiment two:
The preparation method of the sustainable high yield carbon micron tube of present embodiment, realize by following steps:
One, ethylene glycol and urea are mixed for the ratio of 0.5:100 in mass ratio, obtain solid mixture, solid mixture is put into plumbago crucible, the plumbago crucible that then solid mixture will be housed is placed in the gas pressure sintering stove, will to gas pressure sintering stove evacuation to pressure in stove, be 0.1Pa after gas pressure sintering furnace body sealing;
Two, be filled with high pure nitrogen in the gas pressure sintering stove after vacuumizing to step 1, make pressure in the gas pressure sintering stove reach 0.8MPa;
Three, be under the condition of 10 ℃/min at gas pressure sintering stove temperature rise rate, after making the gas pressure sintering furnace temperature rise to 1300 ℃, insulation 90min;
Four, after step 3 insulation finishes, in the adjustable pressure sintering oven, pressure is to 1.5MPa, then to the mixed gas that passes into methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1.7MPa, after continuing insulation 60min at 1300 ℃ of temperature, be cooled to room temperature, namely 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 the carbon micron tube of the present embodiment preparation is every stove 4.5g.
Claims (10)
1. the preparation method of a 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 with ethylene glycol and urea, obtain solid mixture, solid mixture is put into plumbago crucible, the plumbago crucible that then solid mixture will be housed is placed in the gas pressure sintering stove, will to gas pressure sintering stove evacuation to pressure in stove, be 0.1Pa～1Pa after gas pressure sintering furnace body sealing;
Two, be filled with high pure nitrogen or argon gas in the gas pressure sintering stove after vacuumizing to step 1, make pressure in the gas pressure sintering stove reach 0.2MPa～2.5MPa;
Three, be under the condition of 5 ℃/min～30 ℃/min at gas pressure sintering stove temperature rise rate, after making the gas pressure sintering furnace temperature rise to 900 ℃～1500 ℃, insulation 30min～120min;
Four, after the step 3 insulation finishes, in the adjustable pressure sintering oven, pressure is to 0.5MPa～4MPa, again to the mixed gas that passes into methane or methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1MPa～2MPa, after continuing insulation 30min～120min at 900 ℃～1500 ℃ temperature, be cooled to room temperature, namely 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 mix for the ratio of 0.5:100 in mass ratio.
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. the preparation method of according to claim 1,2 or 3 described a kind of sustainable high yield carbon micron tubes, 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 ℃/min.
6. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 5, after it is characterized in that the gas pressure sintering furnace temperature described in step 3 rises to 1100 ℃～1300 ℃, be incubated 60min～90min.
7. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 6, is characterized in that in the adjustable pressure sintering oven described in step 4 that pressure is to 1MPa～1.5MPa.
8. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 7, it is characterized in that described in step 4 again to the mixed gas that passes into methane or methane and ammonia in the gas pressure sintering stove, make pressure in the gas pressure sintering stove reach 1.7MPa.
9. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 8, is characterized in that continuing insulation 60min at 1300 ℃ described in step 4.
10. the preparation method of a kind of sustainable high yield carbon micron tube according to claim 9, is characterized in that the quality percentage composition of the high pure nitrogen described in step 2 〉=99.999%; The quality percentage composition of argon gas 〉=99.999%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310313648.XA CN103387220B (en) | 2013-07-24 | 2013-07-24 | Method for preparing sustainable high-yield carbon microtubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310313648.XA CN103387220B (en) | 2013-07-24 | 2013-07-24 | Method for preparing sustainable high-yield carbon microtubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103387220A true CN103387220A (en) | 2013-11-13 |
| CN103387220B CN103387220B (en) | 2014-12-10 |
Family
ID=49531657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310313648.XA Expired - Fee Related CN103387220B (en) | 2013-07-24 | 2013-07-24 | Method for preparing sustainable high-yield carbon microtubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103387220B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109941984A (en) * | 2019-05-09 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | The preparation method and carbon micron tube of carbon micron tube |
Citations (3)
| 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 |
| JP2005239439A (en) * | 2004-02-24 | 2005-09-08 | National Institute For Materials Science | Method of manufacturing carbon microtube |
| 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 |
-
2013
- 2013-07-24 CN CN201310313648.XA patent/CN103387220B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239439A (en) * | 2004-02-24 | 2005-09-08 | National Institute For Materials Science | Method of manufacturing carbon microtube |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109941984A (en) * | 2019-05-09 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | The preparation method and carbon micron tube of carbon micron tube |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103387220B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104108708A (en) | Nitrogen-doped graphene and preparation method thereof | |
| CN101372325B (en) | Carbon nitride polyporous material and use thereof for hydrogen storage | |
| CN105836729B (en) | The method that Gaseous Detonation method synthesizes iron content CNT | |
| CN104846230A (en) | Preparation method of aluminum-base graphene composite material | |
| CN108380227B (en) | Hydrogen evolution electrocatalytic material and preparation method thereof | |
| CN102491289B (en) | Method for preparing nanoscale magnesium nitride powder | |
| CN105000562B (en) | A kind of preparation method of carborundum hollow ball | |
| CN104944391A (en) | Preparing method of hexagonal boron nitride with high specific surface area | |
| CN113860272A (en) | Preparation method of mesoporous-rich hexagonal boron nitride porous material | |
| CN104961127A (en) | Method for preparing nano graphene powder by plasma chemical vapor synthesis | |
| CN108187712A (en) | A kind of nonmetallic nitridation B catalyst and preparation and application and regeneration method | |
| CN107265416A (en) | The preparation method of pyrolytic boron nitride material | |
| CN103214264B (en) | Method for preparing silicon nitride nanowire-enhanced silicon nitride porous ceramics | |
| CN102443796B (en) | Porous Fe-Al intermetallic compound coating and its preparation method | |
| CN101798077A (en) | Preparation method of hollow carbon sphere with resorcinol and formaldehyde as raw materials | |
| CN105399082A (en) | Chemical vapor deposition equipment and method for preparing graphene film | |
| CN104030265B (en) | Nitrogen-doped carbon nanometer pipe and preparation method thereof | |
| CN102502578B (en) | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template | |
| CN103387220B (en) | Method for preparing sustainable high-yield carbon microtubes | |
| CN102088090B (en) | Method for preparing solid oxide fuel cell SSC cathode by cold spraying technology | |
| CN109663543A (en) | A kind of direct Synthesis boron skin nitrogen core polycrystalline diamond preparation method | |
| CN102765723B (en) | Method for synthesizing KSi hydrogen storage alloy | |
| CN103482610A (en) | Graphene preparation method | |
| CN105253863B (en) | Process for synthesizing hexagonal boron nitride with high specific surface area by using evaporation solvent to guide crystal face control | |
| CN106086811B (en) | It is a kind of to prepare carbon nano pipe array-graphene mixed structure simple and easy method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20160724 |