CN101665997A - Lamellar carbon nanofibre and preparation method thereof - Google Patents
Lamellar carbon nanofibre and preparation method thereof Download PDFInfo
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- CN101665997A CN101665997A CN200910070602A CN200910070602A CN101665997A CN 101665997 A CN101665997 A CN 101665997A CN 200910070602 A CN200910070602 A CN 200910070602A CN 200910070602 A CN200910070602 A CN 200910070602A CN 101665997 A CN101665997 A CN 101665997A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002121 nanofiber Substances 0.000 title abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- 239000002134 carbon nanofiber Substances 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004220 aggregation Methods 0.000 claims description 12
- 230000002776 aggregation Effects 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229930192474 thiophene Natural products 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 241000209094 Oryza Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000000280 densification Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000002041 carbon nanotube Substances 0.000 abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 4
- 238000003475 lamination Methods 0.000 abstract description 3
- 239000002048 multi walled nanotube Substances 0.000 abstract description 3
- 239000002079 double walled nanotube Substances 0.000 abstract 1
- 238000009940 knitting Methods 0.000 abstract 1
- 239000002109 single walled nanotube Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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Abstract
The invention relates to a lamellar fibre material and a preparation method thereof. The lamellar carbon nanofibre has multiple layers and a fibre structure of various cross-sectional shapes. The carbon nanofibre structure in the fibre is single-wall carbon nanotube, double-wall carbon nanotube and multi-wall carbon nanotube or a lamination carbon nanotube formed by the collapse of the carbon nanotubes. The macro structure of the fibre is hollow, solid, flat or crimp, and the like. Reaction carbon source, catalyst and promoter are mixed and added into high-temperature reaction airflow of a reactor, carbon nanotube for catalytic cracking growth is gathered into aggregate of lamellar carbon nanotube fibre in the reaction airflow, and the aggregate is spinned after liquid action or spinned through other online processing. The fibre with a multi-layer structure can be applied to structures, functional devices, knitting, and the like. The preparation method of the invention has simple process, is stable and reliable and can be used for preparing various multi-layer carbon nanofibre materials in industries.
Description
Technical field
The present invention relates to a kind of carbon nano-fiber and technology of preparing thereof, particularly a kind of lamellar fibre material and preparation method thereof.
Technical background
Carbon nano-fiber comprises CNT, by CNT the subside flat-shaped structure that forms and the carbon nanomaterial of carbon-coating structure.Carbon nano-fiber has physical properties such as high strength, high tenacity, high conduction, high heat conduction, the structure of high-specific surface area and functionalization and surface characteristic.These structures, physics, chemistry, mechanics and functional performance are given carbon nano-fiber and are used extremely widely, can be used for preparing high-strength conducting composite material, conductive material, electric field emission and device, sensor, catalyst and carrier, filtration and separate and biomaterial etc.Physics, chemistry, mechanics and the functional performance of carbon nano-fiber with macroscopic carbon fiber material combining nano yardstick of layer structure, the layer structure of high-specific surface area and the stitchability of fiber, can design composite, device and device with it, be to realize high-strength conducting composite material, conductive material, electric field emission and device, sensor, catalyst and carrier, filtration and separate and the ideal material of biomaterial etc.Wherein, hollow multi-layer film structure fiber can be used for absorption, filtration, biological blood vessel, nerve etc., and the multi-layer fiber of profiled-cross-section can be used for preparing composite with special absorbing property etc.
Though available distinct methods prepares the carbon nano-fiber material, the carbon nano-fiber material of preparation is generally the material of random shape at present.Also can prepare the nano fibrous membrane or the macroscopic fibres of macroscopic view by carbon nano-fiber.The preparation approach is generally and prepares nano level carbon fiber or array earlier, prepares macroscopical film and fibrous material by solution dispersion method or wire drawing construction from part again.Fibrous material with these method preparations is a single structure at present.Mikhail etc. can form hollow macroscopic carbon nanotube fiber (Mikhail E by the solution dispersing Nano carbon tubes, et al.Spinning solid and hollow polymer-freecarbon nanotube fibers, Adv.Mater.2005,17,5), but resulting fibre wall is the structure of homogeneous.The chemical vapor flow reaction method is to prepare important method of carbon nano-fiber at present, and this method relates to carbon source is input in the reactor, induces chemical catalysis prepared in reaction carbon nano-fiber.Usually the carbon nano-fiber material of preparing with this method is random shape carbon nano-fiber.United States Patent (USP) (2005/006801-A1) discloses and has a kind ofly prepared the method for macroscopical carbon nano-fiber with chemical gas phase reaction, but report forms the stratiform congeries, and the material of preparation is not a layer structure.Chinese patent CN200710059491.7 and CN 200710059490.2 disclose with the liquid sealed reaction and have added promoter and prepared the method for carbon nano-fiber, but all do not mention preparation lamellar carbon nanofibre material.
Summary of the invention
The purpose of this invention is to provide a kind of lamellar carbon nanofibre and preparation method thereof.The present invention is based on the reaction that vapor phase method prepares carbon nano-fiber, produce the congeries of continuous stratiform, congeries are carried out liquid phase densification and spinning, prepare carbon nano-fiber with layer structure at reaction gas flow.This lamellar carbon nanofibre has multilayer and various cross sectional shape; Carbon nano-structured in the fiber is single wall, double-walled, multi-walled carbon nano-tubes or the lamination carbon nanometer of being subsided and being formed by these CNTs; The macrostructure of fiber is hollow, solid, flat and curling type etc.; The carbon nano-fiber layer is seamless tubular shaped, is concentric combination or laminated.The cross section of fiber and shape depend on the carbon nano-fiber number of plies in fibre diameter and the fiber; The number of plies in the fiber is from which floor to tens of layer, fibre diameter from several microns to the millimeter level, depend on preparation condition and method.This multilayered structure fiber can be used for application such as structure, function element, braiding.Preparation method of the present invention can be used for the various multilayer carbon nano-fiber of preparation of industrialization material.
A kind of layered carbon nano pipe fiber provided by the invention is in the vapor-phase flow catalytic reaction device, to join in the high-temperature reaction airflow of reactor after reaction carbon source, catalyst and the promoter mixing, the CNT of catalytic cracking growth is gathered into the aggregation of layered carbon nano pipe fiber in reaction gas flow, this aggregation is spun or spin in processing through other to make layered carbon nano pipe fiber after liquid effects.
Described carbon source is organic matter, carbonaceous gas or its mixing of carbon containing; Described catalyst comprises that catalyst is the organic matter of iron content, cobalt, nickel etc.; Described promoter is carbon dioxide, water, thiophene and Cu Suan Molybdenum etc. and mixes.
Layered carbon nano pipe fiber cross section provided by the invention is a layer structure, and shape can be hollow ellipse, hollow circle, flat partially or flat partially curling etc.The method for preparing the stratiform fiber provided by the invention relates to carbon source and catalyst is input in the air-flow, in heated air stream, produce the non-individual body of layer structure, the stratiform non-individual body is applied liquid effects, make its densification, form spinnable fiber, fiber is wound on the spindle.
Adopt this invention technology, can directly the stratiform fiber be wound into the formed body with characteristic shape, preparation has macroscopical formed body of ad hoc structure.
In reactant, add promoter and can improve carbon pipe productive rate and purity, promote the assembling of multi-layer film structure.Promoter comprises oxidant and thiophene and Cu Suan Molybdenum and mixing thereof etc. such as carbon dioxide, water.
Other synthesis condition of control carbon nano-fiber multi-layer film structure assembling comprises air-flow and flow.Air-flow is hydrogen, argon gas, nitrogen etc. or its mixing, and hydrogen is preferable.
Adopt liquid phase medium effect stratiform congeries to form the stratiform fiber.Liquid phase medium comprises water, organic liquid or its solution etc.But in solution, add acid, alkali or chemically reactive substance purifying or functionalization stratiform carbon nano-fiber.
Liquid phase effect carbon nano-fiber is implemented in reactor, also can will directly act on the stratiform aggregation after the atomization of liquid, or to the effect of stratiform congeries atomizing of liquids.Liquid phase acts on the reactor that is connected with reactor and implements outward, liquid container can be connected on the reactor, makes the stratiform congeries enter into liquid, forms the fiber of stratiform.Liquid container is used for sealed reaction gas simultaneously and contacts with extraneous air.Liquid container is used for stratiform fiber and the outside device for spinning in the coupled reaction device simultaneously.Spinning can be carried out on liquid level or in the liquid, also can carry out in the reactor outside.Liquid phase effect and spinning carbon nano-fiber congeries can adopt and the similar method of Chinese invention patent (CN101153413), but do not limit and this method.
A kind of layered carbon nano pipe fiber preparation method provided by the invention be synthetic layer structure the carbon nano-fiber congeries after the liquid phase effect spin.The step that mainly comprises comprises:
1) mixed reaction solution with carbon source, catalyst, promoter and water is injected in the vapor-phase flow catalytic reaction device, generates the aggregation of carbon nano-tube fibre at reaction zone.
2) form fiber with liquid effects stratiform aggregation, it is spun.
Described carbon source is the organic matter of carbon containing: ethanol, acetone, ether etc. or its several mixing; Or carbonaceous gas methane, ethene or its mixing.Preferable carbon source is the mixing of acetone and ethanol, the two mass ratio 0.1-3.
Described catalyst is ferrocene, nickel oxalate, ferric acetate and iron chloride etc.The best is a ferrocene, and its mass percent preferable in reactant is 0.05-10%.
Described promoter is water, carbon dioxide, thiophene and Cu Suan Molybdenum etc. and mixes.Preferable promoter is thiophene, and the content mass percent is 0.02-10% in reactant.
Described carbon source content in reaction liquid is 80-99%.
Described temperature of reactor is 900-1600 ℃.
Air-flow velocity in the reactor is the 10-500 mm/second.
Described spinning speed is a per minute 1-30 rice.Preferred per minute 1-20 rice.
The present invention prepares the carbon nano-fiber with layer structure.This lamellar carbon nanofibre has multilayer and various cross sectional shape, carbon nano-structured in the fiber is single wall, double-walled, multi-walled carbon nano-tubes or the lamination CNT that subsided and formed by these CNTs, the macrostructure of fiber is hollow, solid, flat and curling type etc., the carbon nano-fiber layer is seamless tubular shaped, is concentric combination or laminated.The cross section of fiber and shape depend on the number of plies of carbon nano-fiber in fibre diameter and the fiber, the number of plies in the fiber from which floor to tens of layers, fibre diameter from several microns to the millimeter level.This multilayered structure fiber can be used for application such as structure, function element, braiding.Preparation method's technology of the present invention is simple, reliable and stable, can be used for the various multilayer carbon nano-fiber of preparation of industrialization material.
Description of drawings
Fig. 1. preparation lamellar carbon nanofibre embodiment equipment schematic.
Fig. 2. the procedure chart of preparation lamellar carbon nanofibre: reactor side observed stratiform carbon pipe aggregation figure.
Fig. 3. the procedure chart of preparation lamellar carbon nanofibre: the figure of lamellar carbon nanofibre densification in water.
Fig. 4. the procedure chart of preparation lamellar carbon nanofibre: lamellar carbon nanofibre is from spinning an opposite side derived graph.
Fig. 5. the procedure chart of preparation lamellar carbon nanofibre: lamellar carbon nanofibre spins in spinning axle figure.
Fig. 6. be wrapped in continuous lamellar carbon nanofibre product figure on the spindle with what the present invention prepared.
Fig. 7. prepare the carbon nano-fiber surface sweeping Electronic Speculum figure of hollow knot sandwich construction with the present invention.
Fig. 8. prepare lamellar carbon nanofibre surface scan Electronic Speculum figure with the present invention.
Fig. 9. the double-walled carbon pipe nanostructured transmission electron microscope picture of preparing with the present invention.
Figure 10. work out part figure with the lamellar carbon nanofibre that the present invention prepares.
Figure 11. the lamellar carbon nanofibre product figure that arranges for preparing with the present invention.
Figure 12. prepare lamellar carbon nanofibre with the present invention and comprise multilayer membrane structure surface sweeping Electronic Speculum figure.
Figure 13. prepare the flat pattern figure of lamellar carbon nanofibre with the embodiment of the invention 4.
Figure 14. prepare the thermogravimetric curve of lamellar carbon nanofibre with the embodiment of the invention 8.
Based on the experimental facilities of Chinese invention patent (CN101153413), add device for spinning and online treatment device, prepare lamellar carbon nanofibre as example.Equipment comprises tubular reactor, liquid sealing device, device for spinning and online treatment device.Adopt this device preparation lamellar carbon nanofibre, the lamellar carbon nanofibre congeries that form in air-flow enter into liquid medium, form the carbon nano-fiber of stratiform, in liquid or the outside continuous spinning of liquid medium, prepare continuous lamellar carbon nanofibre.Equipment principle such as Fig. 1: 1 spins axle-1,2 spins-2,3 and spins-3,4 nozzles, 5 flanges, 6 quartz ampoules, 7 tube furnaces, 8 cover wound packages rete aggregations, 9 offgas duct, 10 fibers, 11 water, 12 liquid tanks-1,13 acetone, the infrared roasting lamp of 14 liquid tanks-2,15.In the liquid tank 2 acetone is housed, the stratiform fiber is cleaned and densification; Infrared lamp is used for dry spun lamellar carbon nanofibre.
Preparation process is a carbon source for the mixture with ethanol and acetone, is 2 to mix acetone and ethanol with mass ratio, with the ferrocene is catalyst, mass percent with 2% joins in the mixed liquor of ethanol and acetone, with the thiophene is growth accelerator, mass percent with 2% joins in the solution, ultrasonic mixing 10 minutes.Reactor is fed argon gas get rid of air in the reactor, feed the hydrogen of 1000 milliliters of flow velocitys of per minute.The reactant liquor of the above-mentioned preparation injection rate with 10 milliliters of per minutes is injected in the reactor.
The carbon pipe is observed the aggregation (Fig. 2) that forms continuous multilayer tube-in-tube structure film in reaction gas flow, this aggregation enters water tank, through the rotating shaft-1 (Fig. 3) in the water, fiber is derived (Fig. 4) from the rotating shaft opposite side, through spinning axle-2 and liquid tank-2, through infrared roasting lamp oven dry, spin on the axle-3 (Fig. 5) with the speed of spinning of 7 meters of per minutes afterwards.
In order to last method continuous spinning 4 hours, obtain long 1700 meters of lamellar carbon nanofibre, spin at the fiber that spins on the axle, product is seen Fig. 6.
The cross section of the fiber of scanning electron microscopic observation embodiment 1 preparation is hollow, and 120 microns (Fig. 7 a) includes 3 layers of carbon nano-fiber film (Fig. 7 b) to fibre diameter, and fiber surface constitutes (Fig. 8) for the carbon nano-fiber of arranging along machine direction.Layer in the described fiber of transmission electron microscope observing constitutes (Fig. 9) by carbon nano-fiber in it, in the carbon nano-fiber for the CNT of double-walled, (Fig. 9 a) and tubulose (Fig. 9 b) to be the shape that subsides.The purity of described fiber being carried out carbon pipe in the thermogravimetric analysis fiber is 96% (Figure 10).Described fiber woven be prepared into lamellar carbon nanofibre and compile thing (Figure 11).
The fiber production process is with embodiment 1, adds a reciprocating wire rod spinning axle 2 and spin 3 on axle, makes oblique carbon nano-fiber product (Figure 12) of arranging.
Embodiment 4
Preparation process is with embodiment 1, and different is by the rotating shaft direct fabrics in water, obtains the carbon nano-fiber of laminated, and the number of plies is 40, and diameter is 60 microns (Figure 13).
Preparation process is with embodiment 1, and different is with acetone and ethanol mass ratio is 1 mixed carbon source, and making the stratiform carbon pipe nanofiber number of plies is 10, and diameter is 150 micrometer laminar carbon nano-fibers, and this fiber shape of microscopic examination is flat (Figure 14).
Embodiment 6
Preparation process is with embodiment 1, with the speed of spinning of 20 meters of per minutes fiber spun on the axle 3, obtains diameter and be 10 microns lamellar carbon nanofibre, and the fibre section be a circle.
Preparation process is with embodiment 1, is that 1% ferrocene is that catalyst and mass percent are that 0.4% thiophene is a promoter with mass percent, makes lamellar carbon nanofibre, and fibre diameter is 40 microns, and the number of plies is 4 layers.
Preparation process is with embodiment 1, and the hydrogen with 2000 milliliters of per minutes makes stratiform carbon pipe nanofiber, and the number of plies is 4 layers, and diameter is 200 microns.
Embodiment 9
Preparation process replaces to aqueous hydrochloric acid solution with embodiment 1 with the acetone in the liquid tank 2, prepares lamellar carbon nanofibre.
Claims (10)
1, a kind of layered carbon nano pipe fiber, it is characterized in that it is in liquid sealing vapor-phase flow catalytic reaction device, to join in the high-temperature reaction airflow of reactor after reaction carbon source, catalyst and the promoter mixing, the CNT of catalytic cracking growth is gathered into the aggregation of layered carbon nano pipe fiber in reaction gas flow, this aggregation is spun through liquid effects, make layered carbon nano pipe fiber.
2, layered carbon nano pipe fiber according to claim 1, the shape that it is characterized in that this layered carbon nano pipe fiber can be hollow ellipse, hollow circle, flat partially or flat partially structure such as curling.
3, layered carbon nano pipe fiber according to claim 1 is characterized in that described carbon source is organic matter, carbonaceous gas or its mixing etc. of carbon containing;
Described catalyst comprises that catalyst is the organic matter of iron content, cobalt, nickel, comprises ferrocene, cobalt acetate, nickel oxalate or iron chloride etc.;
Described promoter is carbon dioxide, water, thiophene and Cu Suan Molybdenum etc. and mixes.
4, a kind of layered carbon nano pipe fiber preparation method, it is characterized in that it be behind the carbon nano-fiber congeries of synthetic layer structure again through the liquid phase effect, the step that mainly comprises.
1) mixed reaction solution with carbon source, catalyst, promoter and water is injected in the catalytic reactor, generates layered carbon nano pipe aggregate of fibers at reaction zone; The temperature of reactor is 900-1600 ℃.
2) aggregation is through the liquid densification, with spinning of per minute 1-30 rice.
5, method according to claim 4 is characterized in that described carbon source is the organic matter of carbon containing: ethanol, acetone, ether or their mixing or carbonaceous gas methane, ethene or its mixing; Preferable carbon source is the mixing of acetone and ethanol, the two mass ratio 0.1-3: 1.
6, method according to claim 4 is characterized in that described catalyst is ferrocene, nickel oxalate, ferric acetate and iron chloride, and the best is a ferrocene, and the mass percent of catalyst in reactant is 0.05-10%.
7, method according to claim 4 is characterized in that described promoter is water, carbon dioxide, thiophene and Cu Suan Molybdenum and mixing thereof; Preferable promoter is thiophene, and the content mass percent is 0.02-15% in reactant.
8, method according to claim 4 is characterized in that described flow rate of carrier gas is a per minute 200-4000 milliliter.
9, method according to claim 4 is characterized in that described carbon source content in reaction liquid is 80-99%.
10, method according to claim 4 is characterized in that described spinning speed is a per minute 1-30 rice, preferred per minute 5-20 rice.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602918A (en) * | 2012-03-22 | 2012-07-25 | 天津大学 | Graphene band prepared with acid oxidized flat carbon nano-tube and method for preparing graphene band |
| CN103031624A (en) * | 2012-12-03 | 2013-04-10 | 天津大学 | Method for preparing continuous carbon nanotube complex fiber |
| CN103628182A (en) * | 2013-11-29 | 2014-03-12 | 东南大学 | Preparation method of carbon-based nano fiber |
| CN103696243A (en) * | 2013-12-05 | 2014-04-02 | 天津大学 | Composite fiber material of nickel and carbon nano tubes and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100552105C (en) * | 2007-09-04 | 2009-10-21 | 天津大学 | The apparatus and method of producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction |
| CN100540764C (en) * | 2007-09-04 | 2009-09-16 | 天津大学 | Can separate the continuous carbon nano-tube fibre and the preparation technology's method that are |
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