CN101177803A - Method for preparing nano carbon fiber - Google Patents
Method for preparing nano carbon fiber Download PDFInfo
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- CN101177803A CN101177803A CNA2007100361870A CN200710036187A CN101177803A CN 101177803 A CN101177803 A CN 101177803A CN A2007100361870 A CNA2007100361870 A CN A2007100361870A CN 200710036187 A CN200710036187 A CN 200710036187A CN 101177803 A CN101177803 A CN 101177803A
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Abstract
The invention discloses a method for preparing carbon nanofiber, which uses carbon fibers as matrix. The surface of the carbon fibers is pretreated and then catalyst nickel coating and simple substance are prepared on the surface by electroplating method; finally the carbon nanofiber is produced on the carbon fibers by chemical vapor deposition method. The invention comprises the steps that: (1) the surface pretreatment of the carbon fibers; (2) the surface electro nickelling of the carbon fibers; (3) the carbon nanofiber produced by chemical vapor deposition method; (4) drawacharge. The invention is a method for preparing the carbon nanofiber with high quality and high purity without damaging the carbon fiber matrix.
Description
Technical field
The present invention relates to a kind of preparation method of nano carbon fiber.
Background technology
The chemical vapor-phase growing nano carbon fiber generally is vapour-phase pyrolysis and the charcoal fiber of a kind of nanoscale of generating when at high temperature being contacted with transition-metal Fe, Co, Ni and alloy thereof with hydrogen by lower carbon number hydrocarbons.It is except having the characteristic of common vapor-grown carbon fibers, outside low-density, high specific strength, high conduction performance etc., has also that defects count is few, diameter is little, specific area is big and advantage such as hollow tube effect reinforcement.The enhancing body of its general useful as catalysts carrier, lithium rechargeable battery, electrode material, hydrogen storage material and advanced composite materials etc.Nano carbon fiber also can increase electromagnetic scattering and absorbability, the composite that makes with them can have concurrently inhale ripple and bearing load difunctional, therefore become the preferred material of structural wave-absorbing material development, application promise in clinical practice is arranged in microwave absorption field.
At present, according to the mode difference in the catalyst importing reaction system, gas-phase grown nanometer charcoal fiber preparation method can be divided into two classes: matrix method and flowing catalyst method.
The matrix method be with graphite or pottery as matrix, impose the nm-class catalyst particle as growth catalyst, high temperature feeds down hydrocarbon compound gas, hydrocarbons decompose and separate out nano-scale fiber shape charcoal in a side of catalyst granules under the effect of catalyst.This base catalyst method can be prepared high-quality nano carbon fiber.But the preparation of superfine catalyst particle is difficulty very, mainly contains following several method at present and introduce catalyst on matrix: (1) electroless plating method.Chemical plating is a kind of very ripe method, its process route maturation, equipment is simple, but to obtain nano level coating and particle difficult, its technology is difficult to control, and the catalyst layer that is plated in matrix surface is easy to come off.(2) spraying.Spraying is directly catalyst to be made the superfine nano grade particles, then it is sprayed on the matrix.Though this method can be prepared high-quality nano carbon fiber, because the superfine catalyst preparation of granules is very difficult, and in the sprinkling process, catalyst granules distributes can be inhomogeneous, and technology is difficult to control, and its cost is very high.(3) decomposition method.Decomposition method is earlier matrix to be carried out surface treatment in certain strong base solution, carries out immersion for a long time then in containing the nitrate of catalyst elements, at high temperature makes nitrate be decomposed into simple substance catalyst granules and gas at last.This method technology is simple, effectively, but because highly basic is easy to damage matrix, influence the mechanical property of matrix, and the gas of discharging has pollution to air.
The possibility of a large amount of preparation nano carbon fibers is provided on the flowing catalyst method principle.But because catalyst adopts the organo-metallic compound that dissolves in organic solvent, and be made into certain density solution, import reacting furnace, and pass to other reacting gas and diluent gas, its product is collected at the place, gas outlet, so the fiber quality that this method obtains can not show a candle to the good of matrix method.Extremely inhomogeneous as fibre diameter, the ratio shared at nano-scale fiber is few, and is attended by more graininess carbon black in the product.
Summary of the invention
Technical problem to be solved by this invention has provided a kind of method of not damaging the charcoal fibrous matrix and preparing high-quality, highly purified nano carbon fiber.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of nano carbon fiber, with the charcoal fiber as matrix, its basic technology is: earlier preliminary treatment is carried out on the surface of charcoal fiber, prepare catalyst nickel coating and simple substance on its surface by electric plating method again, use method growing nano charcoal fiber on the charcoal fiber of chemical vapour deposition (CVD) at last.Its processing step is:
(1), the surface preparation of charcoal fiber:
Get polypropylene-base, viscose base or pitch based carbon fiber as matrix, the charcoal fiber is generally 1k or 3k; Place it in the organic solution (acetone or benzene) and soaked 3-4 hour, remove one deck organic gel and some impurity of carbon fiber surface, make its active increase, the mass ratio of charcoal fiber and organic solution was generally 1: 5 to 1: 10; Clean the charcoal fiber repeatedly 4-5 time with ultrasonic wave and deionized water then, remove the organic matter that remains in carbon fiber surface; Again the charcoal fiber is put into drying box and dry, temperature remains on 60-70 ℃, and the time is 4-5 hour; In whole process, remain the cleaning of charcoal fiber;
(2), the electroplating nickel on surface of charcoal fiber:
The supply unit of electroplanting device is a dc source, and size of current is 10mA-15mA, can be deposited on the surface of charcoal fiber smoothly to guarantee elemental nickel.It is the nickel sulfate solution of 5%-10% that electroplate liquid adopts concentration.Charcoal fiber after handling is disperseed, and be connected with the negative electrode of electroplating device.Adopt the method for continuous wire that the charcoal fiber is electroplated, wire travelling speed is 20-40cm/min, can guarantee the uniformity of carbon fiber surface electronickelling coating and particle like this.Can adjust the distribution and size of the thickness and the particle of carbon fiber surface nickel dam by changing wire travelling speed.By changing size of current and wire travelling speed, can remain the carbon fiber surface elemental nickel is nanoscale.The charcoal fiber of having electroplated is cleaned 2-3 time repeatedly with ultrasonic wave and deionized water, and the time is generally 1-2min.Fiber after will cleaning is again dried, and temperature is 30-40 ℃, and the time is 5-6 hour, and the ventilating fan of drying box is opened, and reduces the interior air of case and the content of steam as far as possible.
(3), chemical vapor deposition growth nano carbon fiber:
The charcoal fiber that surface electrical is coated with catalyst nickel is placed in the chemical vapor deposition stove.To vacuumizing in the reacting furnace,, begin energising and heat up when pressure during less than 50Pa.The heating-up time of (800 ℃-1000 ℃) is 85-95min from room temperature to the end reaction temperature, is incubated 25-35min then.Furnace pressure is all the time less than 50Pa in temperature-rise period.Gas, reducing gas and the diluent gas that will contain carbon source then mix back input reaction zone.Carbon source is that low melting point micromolecule hydrocarbon is (as CH
4, C3H
6Deng), also can be CO, CO
2, flow is 20-30cm/min; Reducing gas is H
2, flow is 150-200cm/min; Diluent gas is Ar or N
2, flow is 300-400cm/min.In the process of gas-phase grown nanometer charcoal fiber, remain the interior pressure of stove less than 200Pa.The sedimentation time that feeds gas is 2-6 hour.Can control the form that nano carbon fiber is grown by the flow of regulating carbon-source gas, hydrogen and diluent gas, also can control the vary in diameter of nano carbon fiber by the temperature and time of regulating deposition.
(4), come out of the stove:
When sedimentation time reaches technology after the needed time, stop ventilation, close power supply.When temperature reaches room temperature in the stove, take out sample, can obtain needed nano carbon fiber.
Adopt the preparation method of the nano carbon fiber of technique scheme, the advantage and the good effect of its invention are:
(1), adopt the method for electronickelling, can not damage the charcoal fiber.
(2), owing to adopted the method for charcoal fiber wire, change distribution and size that its speed and size of current can be controlled catalyst granules nickel.
(3), the Raney nickel coating of galvanoplastic gained and the cementation force rate between metallic particles and the charcoal fiber a little less than, so the reduction degree of catalyst is bigger, activity is also bigger.
(4), the preparation method is simple, easy to operate, resulting gas-phase grown nanometer charcoal fiber is evenly, amount is many, diameter is evenly distributed, quality height, purity height.
(5), can control the form of nano carbon fiber growth by the flow of regulating carbon-source gas, hydrogen and diluent gas.
(6), can control the vary in diameter of nano carbon fiber by regulating the temperature and time that deposits, to be generally tens nanometers to the hundreds of nanometer.
(7), the complete equipment cost is low, less investment.
In sum, the present invention is a kind of method of not damaging the charcoal fibrous matrix and preparing high-quality, highly purified nano carbon fiber.
Description of drawings
Fig. 1 is an electronickelling equipment schematic diagram;
Fig. 2 is the SEM picture of sample 1;
Fig. 3 is the SEM picture of sample 2.
The specific embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
The electroplanting device schematic diagram is seen accompanying drawing 1, and electroplate liquid 6 is housed in stainless steel oxidation groove 5, and stainless steel oxidation groove 5 is made anode.Fixture 3 is provided with second guide wheel 4, and charcoal fiber 1 passes through stainless steel oxidation groove 5, the first guide wheels 2 again and makes negative electrode through first guide wheel 2, second guide wheel 4.
Embodiment 1:
The HTA charcoal fiber of the 1K that toray company is produced is placed in the acetone soln and soaked 4 hours, remove the glue of fiber surface, the mass ratio of charcoal fiber and organic solution is 1: 5, cleans repeatedly 5 times with ultrasonic wave then, drying is 5 hours in drying box, and temperature is 70 ℃.Compound concentration be 10% nickel sulfate solution as electroplate liquid, current strength is 15mA, wire travelling speed is that 40cm/min carries out electronickelling.The charcoal fiber of electric plated with nickel is cleaned 2 times repeatedly with ultrasonic wave, and the time is 2min, is placed on 40 ℃ of following dryings 5 hours then.The taking-up back installs to be placed on workpiece carries out gas-phase grown nanometer charcoal fiber in the chemical vapor deposition stove.To vacuumizing in the reacting furnace,, begin energising and heat up when pressure during less than 50Pa.1000 ℃ heating-up time is 95min from room temperature to the end reaction temperature, after temperature is elevated to 1000 ℃, is incubated 25min, begin to charge into gas, wherein the propylene flow is 30cm/min, and hydrogen is 200cm/min, nitrogen is 400cm/min, and the pressure in the reacting furnace is controlled at about 200Pa.After deposition 6 hours, stop ventilation, and the blowing out cooling, take out sample 1.Product is a floccule, observes under ESEM, and nano carbon fiber is evenly distributed, and fibre diameter is little, be evenly distributed, and all be tens nanometers, the purity height is seen Fig. 2.
Embodiment 2:
The T-300 charcoal fiber of the 3K that toray company is produced is placed in the benzole soln and soaked 3 hours, remove the glue of fiber surface, the mass ratio of charcoal fiber and organic solution is 1: 10, cleans repeatedly 4 times with ultrasonic wave then, drying is 4 hours in drying box, and temperature is 60 ℃.Compound concentration be 5% nickel sulfate solution as electroplate liquid, current strength is 10mA, wire travelling speed is that 20cm/min carries out electronickelling.The charcoal fiber of electric plated with nickel is cleaned 2 times repeatedly with ultrasonic wave, and the time is 1min.Then, be placed on 30 ℃ of following dryings 6 hours.The taking-up back installs to be placed on workpiece carries out gas-phase grown nanometer charcoal fiber in the chemical vapor deposition stove.To vacuumizing in the reacting furnace,, begin energising and heat up when pressure during less than 50Pa.800 ℃ heating-up time is 85min from room temperature to the end reaction temperature, when temperature is elevated to 800 ℃, insulation, behind the 35min, begin to charge into gas, wherein methane flow is 20cm/min, hydrogen is 150cm/min, argon gas is 300cm/min, in the process of gas-phase grown nanometer charcoal fiber, remains the interior pressure of stove less than 200Pa; After deposition 2 hours, stop ventilation, and the blowing out cooling, take out sample 2.Product is a floccule, observes under ESEM, and nano carbon fiber is evenly distributed, and fibre diameter all is more than 100 nanometer, and the purity height is seen Fig. 3.
In the foregoing description, can be with CO or CO
2Replaced C H
4Or C
3H
6
Claims (3)
1. the preparation method of a nano carbon fiber, with the charcoal fiber as matrix, earlier preliminary treatment is carried out on the surface of charcoal fiber, prepared catalyst nickel coating and simple substance on its surface by electric plating method again, use method growing nano charcoal fiber on the charcoal fiber of chemical vapour deposition (CVD) at last.Its processing step is:
(1), the surface preparation of charcoal fiber:
Get polypropylene-base, viscose base or pitch based carbon fiber as matrix, the charcoal fiber is generally 1k or 3k; Place it in the organic solution and soaked 3-4 hour, remove one deck organic gel and some impurity of carbon fiber surface, the mass ratio of charcoal fiber and organic solution was generally 1: 5 to 1: 10; Clean the charcoal fiber repeatedly 4-5 time with ultrasonic wave and deionized water then, remove the organic matter that remains in carbon fiber surface; Again the charcoal fiber is put into drying box and dry, temperature remains on 60-70 ℃, and the time is 4-5 hour;
(2), the electroplating nickel on surface of charcoal fiber:
Supply unit is a dc source, and size of current is 10mA-15mA, and it is the nickel sulfate solution of 5%-10% that electroplate liquid adopts concentration, the charcoal fiber after handling is disperseed, and be connected with the negative electrode of electroplating device; Adopt the method for continuous wire that the charcoal fiber is electroplated, wire travelling speed is 20-40cm/min; The charcoal fiber of having electroplated is cleaned 2-3 time repeatedly with ultrasonic wave and deionized water, and the time is generally 1-2min; Fiber after will cleaning is again dried, and temperature is 30-40 ℃, and the time is 5-6 hour, and the ventilating fan of drying box is opened, and reduces the interior air of case and the content of steam as far as possible;
(3), chemical vapor deposition growth nano carbon fiber:
The charcoal fiber that surface electrical is coated with catalyst nickel is placed in the chemical vapor deposition stove, to vacuumizing in the reacting furnace, when pressure during less than 50Pa, begins energising and heats up; 800 ℃-1000 ℃ heating-up time is 85-95min from room temperature to the end reaction temperature, is incubated 25-35min then, and furnace pressure is all the time less than 50Pa in temperature-rise period; Gas, reducing gas and the diluent gas that will contain carbon source then mix back input reaction zone; Carbon source is a low melting point micromolecule hydrocarbon, and flow is 20-30cm/min; Reducing gas is H
2, flow is 150-200cm/min; Diluent gas is Ar or N
2, flow is 300-400cm/min, in the process of gas-phase grown nanometer charcoal fiber, remains the interior pressure of stove less than 200Pa; The sedimentation time that feeds gas is 2-6 hour;
(4), come out of the stove:
When sedimentation time reaches technology after the needed time, stop ventilation, close power supply, when temperature reaches room temperature in the stove, take out sample, can obtain needed nano carbon fiber.
2. according to the preparation method of right 1 described nano carbon fiber, it is characterized in that: the organic solution described in the above-mentioned steps (1) is acetone or benzene.
3. according to the preparation method of right 1 or 2 described nano carbon fibers, it is characterized in that: described low melting point micromolecule hydrocarbon is CH
4, C
3H
6, CO or CO
2
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| CNA2007100361870A CN101177803A (en) | 2007-11-21 | 2007-11-21 | Method for preparing nano carbon fiber |
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| CNA2007100361870A CN101177803A (en) | 2007-11-21 | 2007-11-21 | Method for preparing nano carbon fiber |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276282A (en) * | 2011-05-19 | 2011-12-14 | 中南大学 | Preparation method of nanometer carbon fiber reinforced carbon/carbon composite material |
| CN102341234A (en) * | 2009-03-03 | 2012-02-01 | 应用纳米结构方案公司 | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| CN104011287A (en) * | 2011-12-07 | 2014-08-27 | 东邦泰纳克丝欧洲有限公司 | Carbon fiber for composite materials with enhanced conductivity |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| US9573812B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| CN110029382A (en) * | 2019-05-22 | 2019-07-19 | 电子科技大学 | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated |
| CN110424154A (en) * | 2019-08-01 | 2019-11-08 | 山东大学 | A kind of the hydrogen storage method and product of active carbon fiber felt surface metalation and application |
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2007
- 2007-11-21 CN CNA2007100361870A patent/CN101177803A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| US9573812B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US9574300B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| CN102341234A (en) * | 2009-03-03 | 2012-02-01 | 应用纳米结构方案公司 | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
| US10138128B2 (en) | 2009-03-03 | 2018-11-27 | Applied Nanostructured Solutions, Llc | System and method for surface treatment and barrier coating of fibers for in situ CNT growth |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| CN102276282A (en) * | 2011-05-19 | 2011-12-14 | 中南大学 | Preparation method of nanometer carbon fiber reinforced carbon/carbon composite material |
| CN104011287A (en) * | 2011-12-07 | 2014-08-27 | 东邦泰纳克丝欧洲有限公司 | Carbon fiber for composite materials with enhanced conductivity |
| CN110029382A (en) * | 2019-05-22 | 2019-07-19 | 电子科技大学 | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated |
| CN110424154A (en) * | 2019-08-01 | 2019-11-08 | 山东大学 | A kind of the hydrogen storage method and product of active carbon fiber felt surface metalation and application |
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Open date: 20080514 |