CN1948143A - Method of symmetrically growing spiral carbon tube - Google Patents
Method of symmetrically growing spiral carbon tube Download PDFInfo
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- CN1948143A CN1948143A CN200610097488.XA CN200610097488A CN1948143A CN 1948143 A CN1948143 A CN 1948143A CN 200610097488 A CN200610097488 A CN 200610097488A CN 1948143 A CN1948143 A CN 1948143A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 10
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 230000008676 import Effects 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 3
- 235000013980 iron oxide Nutrition 0.000 claims description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011943 nanocatalyst Substances 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract 3
- 238000010668 complexation reaction Methods 0.000 abstract 2
- 229960002089 ferrous chloride Drugs 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 239000010453 quartz Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007233 catalytic pyrolysis Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a method for symmetrically growing spiral carbon tube. Said method includes the following steps: using ferrous chloride of ferrous sulfate as raw material, using citric acid as complexing agent and using absolute alcohol as solvent, making the above-mentioned materials undergo the process of complexation reaction to obtain sol, evaporating and drying said sol to form gel, precalcining said gel at 80-120 deg.C in air to remove organics to form dry gel, then sintering said dry gel at 450 deg.C to obtain oxide nano iron powder body, using said powder body as catalyst precursor and placing it into a ceramic magnetic boat, and placing it into a quartz tube, making reduction reaction at 450 deg.C in H2 atmosphere so as to obtain nano iron catalyst; the mode ratio of ferrous chloride or ferrous sulfate and citric acid is 1:1.0-1:5.0, complexation reaction temperature is 50-90 deg.C, precalcining temperature of dry gel in the air is 300-600 deg.C, its reduction temperature is 300-900 deg.C, reduction time is 3-6 h; closing hydrogen gas, promptly introducing acetylene gas, and heat-insulating for 5-7 h.
Description
One, technical field
The present invention relates to a kind of highly symmetric symmetric growth nanometer spiral carbon tube nanometer and preparation method thereof that has.Especially catalyst nano particle of iron and preparation method thereof.
Two, background technology
The present inventor is that the center is the height symmetric growth with the nano particle of iron in the preparation method of CN200410065511.8 chiral helical carbon fiber, and the particle diameter of carbon fiber is about iron particulate diameter.Its preparation method is that the oxide compound with iron is the complex catalyst precursor thing, this oxide compound is a raw material with iron protochloride or ferrous sulfate, citric acid is a complexing agent, dehydrated alcohol is the preparation method that solvent forms even non-aqueous sol, through forming xerogel at air drying after the complexing, preroasting is removed organism and is obtained in the air.450 ℃ of following reduction promptly obtain the Fe nanoparticle catalyst in H2 atmosphere.Yet, have that the symmetry coiled carbon fibers has more in the scientific research and practicality on meaning.The present invention carries out improved method to relevant described symmetric growth coiled carbon fibers preparation method's patent.
The present invention is great discovery and the important supplement of the applicant about preparation coiled carbon fibers preparation research.Simultaneously, since spiral carbon tube was found, many scientists had foretold and have confirmed the unique physical chemical property of this new carbon structure.As if experiment at present lags far behind theory, because prepared spiral is impure, often contains the straight-bar structure, and mostly is spiral fiber.And present preparation mainly leans against impurity such as mixing sulphur in the catalyzer, and introduces impure gas, and condition is very complicated, and restive.
Three, summary of the invention
The objective of the invention is to: propose a kind of new symmetric growth spiral carbon tube preparation method.Its technology has and does not add any impure gas and impurity, and the characteristic that catalytic pyrolysis acetylene carries out the spiral carbon tube preparation under lower temperature.And propose that a kind of preparation technology is simple, process is controlled easily, the symmetric growth spiral carbon tube preparation method of suitable for mass production.
Technical scheme of the present invention is: symmetric growth spiral carbon tube preparation method, at the iron nano-particle of 100 ± 15 nanometers of hydrogen reducing, import acetylene gas, acetylene imports and holding temperature is 300-600 ℃, be incubated 3-7 hour, make acetylene remain on 100-200Pa in the air chamber of growth.With the nano iron particles is that the center is the height symmetric growth, controls the particle diameter of carbon pipe by control iron particulate diameter.The particle diameter of carbon pipe is about iron particulate diameter.
Especially the temperature of reducing iron oxides nano-powder is 450 ℃ in hydrogen.
With iron protochloride or ferrous sulfate is raw material, citric acid is a complexing agent, dehydrated alcohol is that solvent forms gel through forming colloidal sol after the complexing through evaporation drying, organism is removed in 80-120 ℃ of preroasting in the air, remove organism and form xerogel, the back obtains the ferric oxide nano powder at 450 ℃ of following sintering, this powder is packed into as the complex catalyst precursor thing put into silica tube in the ceramic magnetic boat, again at H
2450 ℃ of following reduction promptly obtain the nanometer iron catalyst in the atmosphere; The mol ratio of iron protochloride or ferrous sulfate and citric acid is 1: 1.0～1: 5.0; The complex reaction temperature is 50-90 ℃, reaction times 3-10 hour; The evaporation drying temperature is 70-100 ℃; Xerogel calcined temperature in air is 300-600 ℃, roasting time 4-10 hour; Reduction temperature is 300-900 ℃ in hydrogen, and the recovery time is 3-6 hour, closes hydrogen, imports acetylene gas at once, is incubated 3-7 hour, and acetylene imports and holding temperature is 300-600 ℃.The temperature of reducing iron oxides nano-powder is 450 ℃ in the hydrogen, and the recovery time is 3-5 hour, closes hydrogen, imports acetylene gas at once, is incubated 3-10 hour, and acetylene imports and holding temperature is 450 ℃.
The present invention adopts iron to make catalyzer, and this catalyzer prepares in conjunction with hydrogen reduction method by the collosol and gel of non-water approach.Therefore, iron nano-particle is tiny and even, compares with the big iron particle of bibliographical information, has bigger catalytic activity.
With the iron particle of method preparation of the present invention, size distribution is even, generally is about 100 ± 15 nanometers.The iron of bibliographical information is done the nanotube that catalyzer can only catalytic pyrolysis acetylene produces carbon, and temperature is higher, never appear in the newspapers and produce the symmetric growth spiral carbon tube, let alone practical application.And the particle diameter of the present invention preparation is about the iron nano-particle of 100 ± 15 nanometers, has unique catalytic performance, can be under 450 ℃ of temperature cracking acetylene fully, produce the symmetric growth spiral carbon tube.
Molysite commonly used is iron protochloride or ferrous sulfate, and complexing agent also can adopt oxalic acid except that citric acid.
Product with the present invention preparation carries out structure and performance characterization by following means: utilize the JEM-200CX transmission electron microscope (TEM) that Japanese JEOL company produces and the shape and size of FE-SEM direct viewing product; Adopt infrared spectra, analyze acetylene cracking situation.
Iron protochloride of the present invention or ferrous sulfate are initial feed, and its concentration is 0.03～0.5mol/L (in solvent and complexing agent) thereby makes the complex catalyst precursor thing for preparing, makes the oxide nano particles of iron have bigger diameter.
Therefore the present invention adopts non-aqueous solvent, effectively prevents the generation of the hard aggregation of nanoparticle, and the nanoparticle of gained iron has smaller particle size and narrower size distribution, therefore has bigger and catalytic activity uniqueness.Preparation technology is simple, process is controlled suitable for mass production easily.It is the center that the product that the inventive method prepares has with the catalyzer, two symmetric growth spiral carbon tubes of growth on each catalyst particle, and present highly symmetric characteristics.The spiral carbon tube production of preparing in addition has good microwave absorbing property, may have good application aspect the lightweight microwave absorbing material.
A large amount of experiment confirms by the inventor: the final pattern of product also has relation very closely with the size of granules of catalyst.The inventive method is that the strong of existing method replenished, and simpler, easy to control, and the output of gained spiral tube is very high.
Four, description of drawings
Fig. 1 is the typical electron microscopy observation result of the product of example 1 preparation, and product has fabulous symmetric growth spiral tube structure as seen from the figure, and two symmetric carbon pipes have the characteristics of opposite symmetric growth, and one is left hand, and another root is the right hand.
Fig. 2 is the field emission scanning electron microscope observed result of the product for preparing in example 1 preparation process, and as can be seen from the figure, product is a large amount of spiral symmetric growth carbon pipe, and diameter is comparatively even.
Fig. 3 is the XRD result of the product of example 1 preparation, as can be seen from the figure, has the peak of very strong graphite carbon, shows that acetylene is cracked into graphite carbon fully.Complete cracking hydrocarbon chain shows that the Fe nanometer particles of preparation has big catalytic activity under this relatively low temperature.
Fig. 4 is in example 2 preparation process, and the XRD result of the product that annealing obtains under 750 ℃ of temperature illustrates that iron-carbon removes alloy substantially fully and changes iron under this temperature, illustrates that this annealing temperature is very big to the influence of product component.
Fig. 5 is the scanning electron microscopic observation result of the product of example 3 preparations, the result show reduction temperature and example 1 the same be 450 ℃, the catalytic pyrolysis temperature is also the same with example 1 to be 450 ℃, but the symmetric growth spiral carbon tube of product is elongated, is very long symmetric growth spiral carbon tube.Show that catalyst consumption has a significant impact the growth of spiral carbon tube.
Fig. 6 is the scanning electron microscopic observation result of the product of example 4 preparation, the result show reduction temperature and example 1 the same be 450 ℃, the catalytic pyrolysis temperature is also the same with example 1 to be 450 ℃, but product becomes a large amount of straight-bars and a spot of symmetric growth spiral carbon tube mixture.Show that catalyst consumption has a significant impact the content of spiral carbon tube in the product.
Five, embodiment
Below be embodiments of the invention (agents useful for same is a chemical pure among the embodiment).
Embodiment 1: under the strong mixing, with 0.03mol FeCl
24H
2O and 0.045mol citric acid are dissolved in the 100mL dehydrated alcohol, and 60 ℃ continue to stir 6 hours, form homogeneous transparent colloidal sol; 80 ℃ of evaporation dryings are until generating xerogel; Xerogel 450 ℃ of preroasting 3 hours in air is got an amount of this oxide compound then and is placed tube furnace to place 450 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours.Close hydrogen then, import acetylene gas at once, 450 ℃ of down insulations 6 hours, postcooling is to room temperature, the carbon pipe electron microscopy observation that obtains the results are shown in Figure 1, an emission surface sweeping electron microscopic observation the results are shown in Figure 2 and XRD the results are shown in Figure 3.Same molar oxalic acid also can.Make acetylene remain on 150Pa in the air chamber of growth.With the nano iron particles is that the center is the height symmetric growth, controls the particle diameter of carbon pipe by control iron particulate diameter.The particle diameter of carbon pipe is about iron particulate diameter.
Embodiment 2: under the strong mixing, with 0.03mol FeCl
24H
2O and 0.045mol citric acid are dissolved in the 100mL dehydrated alcohol, and 60 ℃ continue to stir 6 hours, form homogeneous transparent colloidal sol; 80 ℃ of evaporation dryings are until generating xerogel; Xerogel 450 ℃ of preroasting 3 hours in air is got an amount of this oxide compound then and is placed 450 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours.Close hydrogen then, import acetylene gas at once, 450 ℃ of down insulations 6 hours, postcooling is to room temperature, after be rapidly heated to 750 ℃, close acetylene gas then, import argon gas at once, 750 ℃ of insulations 4 hours down, postcooling is to room temperature, the XRD that obtains the results are shown in Figure 4.
Embodiment 3: experimentation is the same with embodiment 1 with condition, but catalyst consumption is 3 times of embodiment 1, and the carbon pipe scanning electron microscope observation that obtains the results are shown in Figure 5.600 ℃ the insulation 3 hours the reduction also can, acetylene remains on 100Pa.
Embodiment 4: experimentation is the same with embodiment 1 with condition, but catalyst consumption is 6.5 times of embodiment 4, and the carbon pipe electron microscopy observation that obtains the results are shown in Figure 6.400 ℃, be incubated reduction in 7 hours and also can.
Claims (5)
1, the method for symmetric growth spiral carbon tube, the iron nano-particle that it is characterized in that 100 ± 15 nanometers under hydrogen reducing imports acetylene gas, and acetylene imports and holding temperature is 300-600 ℃, be incubated 3-7 hour, make acetylene remain on 100-200Pa in the air chamber of growth.
2, the method for symmetric growth spiral carbon tube according to claim 1 is characterized in that controlling the particle diameter of carbon pipe by controlling iron particulate diameter.
3,, it is characterized in that iron protochloride or ferrous sulfate are initial feed, thereby its concentration is the complex catalyst precursor thing that 0.03～0.5mol/L makes preparation by the method for the described symmetric growth spiral carbon tube of claim 2.
4, the method of symmetric growth spiral carbon tube according to claim 1, it is characterized in that by preparing the iron nanocatalyst particle symmetric growth spiral carbon tube of 100 ± 15 nanometers, with iron protochloride or ferrous sulfate is raw material, citric acid is a complexing agent, dehydrated alcohol is that solvent forms gel through forming colloidal sol after the complexing through evaporation drying, organism is removed in 80-120 ℃ of preroasting in air, remove organism and form xerogel, the back obtains the ferric oxide nano powder at 450 ℃ of following sintering, this powder packed into as the complex catalyst precursor thing put into silica tube in the ceramic magnetic boat, again at H
2450 ℃ of following reduction promptly obtain the nanometer iron catalyst in the atmosphere; The mol ratio of iron protochloride or ferrous sulfate and citric acid is 1: 1.0～1: 5.0; The complex reaction temperature is 50-90 ℃, reaction times 3-10 hour; The evaporation drying temperature is 70-100 ℃; Xerogel calcined temperature in air is 300-600 ℃, roasting time 4-10 hour; Reduction temperature is 300-900 ℃ in hydrogen, and the recovery time is 3-6 hour, closes hydrogen, imports acetylene gas at once, is incubated 3-10 hour, and it is 300-600 ℃ that acetylene imports holding temperature, makes acetylene remain on 100-200Pa in the air chamber.。
5, the method for symmetric growth spiral carbon tube according to claim 3, the temperature that it is characterized in that reducing iron oxides nano-powder in the hydrogen is 450 ℃, and the recovery time is 3-5 hour, closes hydrogen, import acetylene gas at once, it is 450 ℃ of insulations 3-10 hour that acetylene imports holding temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610097488.XA CN1948143A (en) | 2006-11-13 | 2006-11-13 | Method of symmetrically growing spiral carbon tube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610097488.XA CN1948143A (en) | 2006-11-13 | 2006-11-13 | Method of symmetrically growing spiral carbon tube |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885483A (en) * | 2010-07-14 | 2010-11-17 | 南京大学 | Layered carbon nano rod and preparation method thereof |
| CN102515092A (en) * | 2011-12-02 | 2012-06-27 | 中国科学院化学研究所 | Method for manufacturing micro-spring |
| CN112624089A (en) * | 2021-01-16 | 2021-04-09 | 桂林理工大学 | Method for synthesizing spiral carbon nano tube-carbon nano tube heterojunction |
| CN112938928A (en) * | 2021-02-03 | 2021-06-11 | 大连理工大学 | Carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance and preparation method and application thereof |
-
2006
- 2006-11-13 CN CN200610097488.XA patent/CN1948143A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885483A (en) * | 2010-07-14 | 2010-11-17 | 南京大学 | Layered carbon nano rod and preparation method thereof |
| CN102515092A (en) * | 2011-12-02 | 2012-06-27 | 中国科学院化学研究所 | Method for manufacturing micro-spring |
| CN102515092B (en) * | 2011-12-02 | 2014-06-25 | 中国科学院化学研究所 | Method for manufacturing micro-spring |
| CN112624089A (en) * | 2021-01-16 | 2021-04-09 | 桂林理工大学 | Method for synthesizing spiral carbon nano tube-carbon nano tube heterojunction |
| CN112938928A (en) * | 2021-02-03 | 2021-06-11 | 大连理工大学 | Carbon matrix spiral chiral structure metamaterial with abnormal ferromagnetic performance and preparation method and application thereof |
| CN112938928B (en) * | 2021-02-03 | 2023-10-20 | 大连理工大学 | Carbon matrix spiral chiral sequence metamaterial with abnormal ferromagnetic performance, and preparation method and application thereof |
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