CN101899726B - Method for preparing nano-carbon fibers - Google Patents
Method for preparing nano-carbon fibers Download PDFInfo
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- CN101899726B CN101899726B CN2010102552573A CN201010255257A CN101899726B CN 101899726 B CN101899726 B CN 101899726B CN 2010102552573 A CN2010102552573 A CN 2010102552573A CN 201010255257 A CN201010255257 A CN 201010255257A CN 101899726 B CN101899726 B CN 101899726B
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Abstract
The invention discloses a method for preparing nano-carbon fibers. The linear and spiral nano-carbon fibers are prepared by catalyzing C2H2 under the catalysis condition. The method comprises the following steps of: (a) dispersing cupric tartrate powder on a ceramic boat substrate carrier in an amount of between 0.5 and 2.5mg/cm<2>; (b) putting the ceramic boat filled with the cupric tartrate powder in the middle of a quartz tube in a horizontal furnace, controlling the temperature of the heating furnace to between 270 and 390 DEG C, and decomposing the cupric tartrate for 15 to 60 minutes ina decomposing atmosphere to obtain catalyst particles; and (c) controlling the reaction temperature of between 195 and 274 DEG C to in-situ prepare the linear or spiral nano-fibers on the catalyst particles by adopting acetylene gas serving as a reactant. The size and geometric appearance of the catalyst particles are influenced by different decomposition atmospheres of the catalyst precursor, sothat the nano-carbon fibers with different appearances can be prepared by catalyzing the acetylene.
Description
Affiliated technical field
The present invention relates to a kind of carbon nano-fiber preparation methods, particularly linear and spiral nano fiber production method.
Background technology
Coiled carbon fibers has caused colleagues' extensive concern since Davis (1953) finds.This is because coiled carbon fibers is except that having general properties of carbon (low-density, high specific strength, heat resistance, electric heating conduction, chemical stability); Also have performances such as elasticity, resistance to impact, absorbing property and hydrogen gas storage, can be applicable to fields such as wave-absorbing and camouflage, energy storage, micromechanical component, sensor and electrode material.
The spiral shell of the coiled carbon fibers of report directly has micron and nanoscale at present.The micron coiled carbon fibers patent report as: Chinese patent (publication number CN 1327093A) is characterized in: through control C
2H
2/ H
2And C
2H
2/ N
2Throughput and ratio, prepare elastomeric little screw carbon fibre at 700-800 ℃; Chinese patent (publication number CN 101451278A) is characterized in that: adopting chemical plating process to form ni-p alloy coating at graphite surface is catalyst, control C
2H
2/ H
2Throughput and ratio are prepared single, double coiled carbon fiber dimension at 600-800 ℃.
The coil diameter is that the domestic preparation method of nano level coiled carbon fibers mainly contains: Chinese patent (publication number CN 1641083A); Be characterized in: make the nano-structured method of copper catalyst particle through electrochemistry template and vacuum sputtering, make the nanometer coiled carbon fibers at 750 ℃ of left and right sides catalyzing acetylenes; Chinese patent (publication number CN 1517458A); It is characterized in that: employing hydrogen is that carrier gas, acetylene are that carbon source, nickel foam are catalyst; Add when adding carbon source and contain growth promoter of sulfur, prepare CNT, nanofiber or helical carbon fiber at a lower temperature; (publication number CN 1995503A) is characterized in that: employing acetylene is that carbon source, hydrogen are that carrier gas, nitrogen or argon gas are that diluent gas, nickel plate are catalyst, PCl
3Be co-catalyst, prepare spiral nano carbon fiber at a lower temperature; Periodical " carbon " (2003,41:3063-3074) report that the copper nanoparticle that Cui Zuolin professor seminar obtained at 250 ℃ of cracking cupric tartrates in 10 minutes is a catalyst, catalyzing acetylene prepares a kind of novel coiled carbon fibers between 250-400 ℃.SCI [2005,26 (1): 5-8] has reported that again this seminar uses the nanometer copper-nickel alloy to be catalyst, prepares the spiral nanometer carbon fiber of symmetric growth through the catalyse pyrolysis of acetylene afterwards.But preparing, they need vacuum condition in the catalyst process perhaps by hydrogen arc plasma method.More than these methods, need to adopt multistage step, or need special catalyst aid or expensive equipment, the cost of preparation nanometer coiled carbon fibers is higher.
Summary of the invention
Above shortcoming in view of prior art the purpose of this invention is to provide the method that a kind of technology is simple, the high and low cost of output prepares linear and spiral nano carbon fiber.
The objective of the invention is to realize through following means:
A kind of method for preparing carbon nano-fiber, catalysis C under catalytic condition
2H
2Obtain carbon nano-fiber, by horizontal heater be arranged in the horizontal heater and have the in-situ preparing of accomplishing said carbon nano-fiber in the equipment that built-in quartz ampoule that external source of the gas imports and exports constitutes, comprise following steps:
(a). the cupric tartrate powder is scattered in the ethanol, is sprayed on the ceramic bateau after ultrasonic 10-30 minute, and ethanol volatilization back cupric tartrate powder is dispersed on the ceramic bateau substrate carrier as catalyst precursor;
(b). the ceramic bateau that the cupric tartrate powder is housed that (a) obtained is put into the said quartz ampoule middle part of diameter 45mm, length 1300mm; Then quartz ampoule is put into the tubulose horizontal heater; Quartz ampoule feeds selected decomposition atmosphere; Heating and control temperature are 270 ℃-390 ℃, keep 15-60 minute, and the catalyst precursor decomposition obtains the nano copper particle as catalyst;
(c). 195 ℃-274 ℃ of regulation and control tubulose horizontal heater temperature; Quartz ampoule feeds reactant acetylene with the 20-60ml/min flow; Feed after 30-90 minute and stop the gas cessation reaction,, prepare linear or spiral nano carbon fiber through regulating and control the composition of said decomposition atmosphere.
Adopt means of the present invention, different through the decomposition atmosphere of catalyst precursor, influence the size of catalyst granules, how much patterns, thereby catalyzing acetylene obtains the carbon nano-fiber of different-shape.The present invention can be as required carbon nano-fiber (linear or spirality), regulate and control the decomposition atmosphere of catalyst precursor, mainly be divided into five types:
Last table shows, adopts the inventive method, when the decomposition atmosphere of decomposition cupric tartrate is chosen to be one of argon gas, nitrogen under the said normal pressure, obtains said aim carbon fiber and is mainly linear nanofiber; When decomposition atmosphere is chosen to be acetylene, obtains said aim carbon fiber and be mainly the spiral nano fiber; When decomposition atmosphere is chosen to be hydrogen, prepare linear and nanofibers two kinds of mixing of spirality.
Description of drawings
Figure 1A is the typical scan Electronic Speculum figure of embodiment 1 preparation catalyst.
Figure 1B is the typical scan Electronic Speculum figure of embodiment 1 preparing product.
Fig. 2 A is the typical scan Electronic Speculum figure of embodiment 2 preparation catalyst.
Fig. 2 B is the typical scan Electronic Speculum figure of embodiment 2 preparing products.
Fig. 3 is the typical scan Electronic Speculum figure of embodiment 3 preparing products.
Fig. 4 is the typical scan Electronic Speculum figure of embodiment 4 preparing products.
Fig. 5 A is the typical scan Electronic Speculum figure of embodiment 5 preparation catalyst.
Fig. 5 B is the typical scan Electronic Speculum figure of instance 5 preparing products.
Fig. 6 is fiber infared spectrum of cracking 2h afterproduct in the nitrogen under different temperatures.
Fig. 7 is that spiral fiber content is fiber typical scan Electronic Speculum figure behind the cracking 4h in 900 ℃ of nitrogen of 90%.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Said cupric tartrate is a catalyst precursor, is scattered in the amount ranges 0.5-2.5mg/cm of ceramic boat substrate carrier
2Presoma decomposition atmosphere is one or more in argon gas (99%-99.999%), nitrogen (99%-99.99%), hydrogen (99.9%-99.99%) or the acetylene gas (98%-99.9%).
Embodiment 1: get 40mg cupric tartrate powder and join in the absolute ethyl alcohol of 5mL, after ultrasonic 10 minutes, be transferred in the ceramic bateau; After treating that absolute ethyl alcohol volatilizees automatically, the cupric tartrate powder is dispersed in ceramic boat (floor space 16.5cm
2) on; Place the quartz ampoule middle part to the ceramic boat that is dispersed with catalyst precursor, the inspection air-tightness also charges into argon gas (or nitrogen) 150ml/min discharge in 20 minutes air; The bedroom stove is heated up (1-2 ℃/min) to 270 ℃, constant temperature 30 minutes, cupric tartrate are decomposed into copper particle (like Figure 1A); Stop to charge into argon gas, introduce acetylene 40ml/min, react and stop to feed acetylene after 60 minutes, introduce termination gas argon gas cessation reaction; Cool to room temperature with the furnace, take out sample, its microcosmic typical case's pattern such as Figure 1B, spiral fiber content is about 3%.
In actual experiment, stopping gas adopts nitrogen to have same effect.
Figure 1A is the typical scan electron microscopy observation result of embodiment 1 preparation catalyst, and the pattern of visible catalyst is irregular from figure, has granularly and bar-shaped, and average grain diameter is 200nm.Figure 1B is the typical scan electron microscopy observation result of instance 1 preparing product, and visible product has the higher purity linear fiber from figure, and the diameter of fiber is 150-300nm.
Embodiment 2: get 30mg cupric tartrate powder and join in the absolute ethyl alcohol of 5mL, after ultrasonic 15 minutes, be transferred in the ceramic bateau; After treating that absolute ethyl alcohol volatilizees automatically, the cupric tartrate powder is dispersed in ceramic boat (floor space 16.5cm
2) on; Place the quartz ampoule middle part to the ceramic boat that is dispersed with catalyst precursor, the inspection air-tightness also charges into hydrogen 150ml/min discharge in 20 minutes air; The bedroom stove is slowly heated up (2-3 ℃/, be cooled to 240 ℃ behind the constant temperature 20min min) to 300 ℃, cupric tartrate is decomposed into copper particle (like Fig. 2 A); Stop to charge into hydrogen, introduce acetylene 40ml/min, react and stop to feed acetylene after 60 minutes, introducing argon gas cessation reaction; Cool to room temperature with the furnace, take out sample, its microcosmic typical case's pattern such as Fig. 2 B, spiral fiber content is about 55%.
Fig. 2 A is the typical scan electron microscopy observation result of embodiment 2 preparation catalyst, and the pattern of visible catalyst is the reunion shape from figure, and the granule average grain diameter is 60nm.Fig. 2 B is the typical scan electron microscopy observation result of instance 2 preparing products, and visible product contains linear and the spiral nano fiber from figure, and the diameter of fiber is 100-150nm.
Embodiment 3: get 20mg cupric tartrate powder and join in the absolute ethyl alcohol of 10mL, after ultrasonic 20 minutes, be transferred in the ceramic bateau; After treating that absolute ethyl alcohol volatilizees automatically, the cupric tartrate powder is dispersed in ceramic boat (floor space 16.5cm
2) on; Place the quartz ampoule middle part to the ceramic boat that is dispersed with catalyst precursor, the inspection air-tightness also charges into mist N
2/ H
2, (N
2/ H
2=3, H
2=30ml/min) discharged air in 25 minutes; The bedroom stove is slowly heated up (1-2 ℃/min) to 320 ℃, constant temperature 10min is cooled to 230 ℃, and cupric tartrate is decomposed into copper particle (like Fig. 3 A); Stop to charge into mist N
2/ H
2, introduce acetylene 60ml/min, react and stop to feed acetylene after 90 minutes, introducing nitrogen cessation reaction; Cool to room temperature with the furnace, take out sample, its microcosmic typical case's pattern such as Fig. 3, spiral fiber content is about 15%.
Fig. 3 is the scanning electron microscope observation result of embodiment 3 preparation catalyst, and visible product contains linear and the spiral nano fiber from figure, and the diameter of fiber is 100-300nm.
Fig. 5 A is the typical scan electron microscopy observation result of embodiment 3 preparation catalyst, and the pattern of visible catalyst is regular from figure, and size is single, and average grain diameter is 50nm.Fig. 5 B is the scanning electron microscope observation result of embodiment 3 preparing products, and visible product contains high-purity spiral nano-fibre from figure, and the diameter of fiber is about 100nm.
Embodiment 4: get 15mg cupric tartrate powder and join in the absolute ethyl alcohol of 10mL, after ultrasonic 20 minutes, be transferred in the ceramic bateau; After treating that absolute ethyl alcohol volatilizees automatically, the cupric tartrate powder is dispersed in ceramic boat (floor space 16.5cm
2) on; Place the quartz ampoule middle part to the ceramic boat that is dispersed with catalyst precursor, the inspection air-tightness also charges into mist N
2/ H
2, (N
2/ H
2=3, H
2=30ml/min) discharged air in 25 minutes; The bedroom stove is slowly heated up (2-3 ℃/min) to 390 ℃, constant temperature was cooled to 195 ℃ in 10 minutes, and cupric tartrate is decomposed into copper particle (like Fig. 3 A); Stop to charge into mist N
2/ H
2, introduce acetylene 20ml/min, react and stop to feed acetylene after 30 minutes, introducing nitrogen cessation reaction; Cool to room temperature with the furnace, take out sample, its microcosmic typical case's pattern such as Fig. 4, spiral fiber content is about 75%.
Fig. 4 is the scanning electron microscope observation result of embodiment 4 preparation catalyst, and visible product contains linear and the spiral nano fiber from figure, and the diameter of fiber is 100-150nm.
Embodiment 5: get 10mg cupric tartrate powder and join in the absolute ethyl alcohol of 5mL, after ultrasonic 30 minutes, be transferred in the ceramic bateau; After treating that absolute ethyl alcohol volatilizees automatically, the cupric tartrate powder is dispersed in ceramic boat (floor space 16.5cm
2) on; Place the quartz ampoule middle part to the ceramic boat that is dispersed with catalyst precursor, the inspection air-tightness also charges into acetylene 150ml/min discharge in 20 minutes air; The acetylene gas flow is transferred to minimum, and guarantee not produce the suck-back phenomenon in the offgas duct; The bedroom stove is slowly heated up (0.5-2 ℃/min) to 270 ℃, introduce acetylene 40ml/min react and stops to feed acetylene after 60 minutes, introducing argon gas cessation reaction; Cool to room temperature with the furnace, take out sample, its microcosmic typical case's pattern such as Fig. 5 B.Adopt mist (acetylene/hydrogen=1/10), at 270 ℃ of cracking 15min, observe catalyst granules pattern such as Fig. 5 A, regular particles, size are single, and average grain diameter is about 50nm, and spiral fiber content is about 98%.
The fiber (comprising linear and spirality) that embodiment 1 prepares to the instance 5 obtains corresponding linear or helical carbon fiber behind the atmospheric cracking 1-4h in 800-1000 ℃ of nitrogen.Fig. 6 is fiber infared spectrum of cracking 2h afterproduct in the nitrogen under different temperatures.From figure, can draw after temperature reaches 800 ℃, fiber carbonization is corresponding carbon fiber.
Fig. 7 is that spiral fiber content is fiber figure of the SEM behind the cracking 4h in 900 ℃ of nitrogen of 90%.From figure, can learn that the spiral of fiber remains intact.
When the cracking atmosphere of cracking cupric tartrate was one of argon gas, nitrogen under the said normal pressure, the said aim carbon fiber that obtains was high-purity linear nanofiber (95%-99%); When cracking atmosphere was acetylene, the said aim carbon fiber that obtains was high-purity spiral nano fiber (95%-99%); When cracking atmosphere is hydrogen, can prepare linear and nanofibers two kinds of mixing of spirality.
Linear content with spirality fiber can be regulated between 5%～95% respectively through the proportioning situation of presoma decomposition atmosphere.With the spiral fiber explanation, be N when presoma decomposes atmosphere
2And H
2, and N
2/ H
2=0.01～100, spirality fiber content is 5%～40%; When presoma decomposes atmosphere is N
2And H
2, and C
2H
2/ H
2=0.01～100, spirality fiber content is 40%～95%.
Claims (2)
1. method for preparing carbon nano-fiber, catalysis C under catalytic condition
2H
2Obtain carbon nano-fiber, by horizontal heater be arranged in the horizontal heater and have the in-situ preparing of accomplishing said carbon nano-fiber in the equipment that built-in quartz ampoule that external source of the gas imports and exports constitutes, comprise following steps:
(a). the cupric tartrate powder is scattered in the ethanol, is sprayed on the ceramic bateau after ultrasonic 10-30 minute, and ethanol volatilization back cupric tartrate powder is dispersed on the ceramic bateau substrate carrier as catalyst precursor;
(b). the ceramic bateau that the cupric tartrate powder is housed that (a) obtained is put into the said quartz ampoule middle part of diameter 45mm, length 1300mm; Then quartz ampoule is put into the tubulose horizontal heater; Quartz ampoule feeds selected decomposition atmosphere; Heating and control temperature are 270 ℃-390 ℃, keep 15-60 minute, and the catalyst precursor decomposition obtains the nano copper particle as catalyst;
(c). 195 ℃-274 ℃ of regulation and control tubulose horizontal heater temperature, quartz ampoule feeds reactant acetylene with the 20-60ml/min flow, feeds after 30-90 minute to stop the gas cessation reaction;
Through regulating and control the composition of said decomposition atmosphere, prepare linear or spiral nano carbon fiber: when the decomposition atmosphere of decomposition cupric tartrate is chosen to be one of argon gas, nitrogen under the said normal pressure, obtains said aim carbon fiber and be mainly linear nanofiber; When the decomposition atmosphere of decomposition cupric tartrate is chosen to be acetylene under the said normal pressure, obtains said aim carbon fiber and be mainly the spiral nano fiber; When the decomposition atmosphere of decomposition cupric tartrate is chosen to be hydrogen under the said normal pressure, prepare linear and nanofibers two kinds of mixing of spirality.
2. the method that prepare carbon nano-fiber according to claim 1 is characterized in that: the amount ranges that said cupric tartrate powder is scattered in the ceramic boat substrate carrier is 0.5-2.5mg/cm
2
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| CN102320590B (en) * | 2011-06-22 | 2013-01-23 | 天津大学 | Method for directly growing single and double-spiral nano carbon fibers on copper matrix |
| CN102367164A (en) * | 2011-10-27 | 2012-03-07 | 无锡英普林纳米科技有限公司 | One-dimensional microstructural array and preparation method thereof |
| CN103276476B (en) * | 2013-04-09 | 2015-03-25 | 西南交通大学 | Method for preparing nano-carbon fibers by T-ZnOw surface in-situ polymerization |
| CN103590141B (en) * | 2013-08-26 | 2015-09-16 | 国家纳米科学中心 | A kind of silver-glutathione chirality nanofiber and preparation method thereof |
| CN103723703B (en) * | 2014-01-06 | 2015-07-15 | 四川理工学院 | Method for preparing helical carbon nanotube at low temperature |
| CN104157834B (en) * | 2014-08-26 | 2017-03-08 | 四川理工学院 | Spiral sodium rice carbon fiber is used as application and the GND preparation method of lithium ion battery negative material |
| CN105070914B (en) * | 2015-07-27 | 2017-10-20 | 四川理工学院 | The preparation method of DNA double helical form carbon nano-fiber, using and lithium ion battery negative material preparation method |
| CN112479730A (en) * | 2020-12-17 | 2021-03-12 | 中南大学 | Preparation method of curved carbon nanofiber reinforced C/C composite material |
| CN113463226B (en) * | 2021-06-30 | 2023-02-14 | 杭州富通通信技术股份有限公司 | Cable sheath filler and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643193A (en) * | 2002-05-22 | 2005-07-20 | 昭和电工株式会社 | Process for producing vapor-grown carbon fibers |
| CN1995503A (en) * | 2006-01-06 | 2007-07-11 | 北京化工大学 | Method for preparing spiral nano carbon fiber |
| CN101314129A (en) * | 2008-07-04 | 2008-12-03 | 浙江大学 | Non-carrier yellow brass catalyst for preparing stephanoporate carbon fiber, preparation and process of using |
| CN101384358A (en) * | 2006-02-16 | 2009-03-11 | 拜尔材料科学股份公司 | Continuous preparation method of catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3071571B2 (en) * | 1992-07-24 | 2000-07-31 | 住友ベークライト株式会社 | Method for producing vapor grown carbon fiber |
| US9725314B2 (en) * | 2008-03-03 | 2017-08-08 | Performancy Polymer Solutions, Inc. | Continuous process for the production of carbon nanofiber reinforced continuous fiber preforms and composites made therefrom |
-
2010
- 2010-08-17 CN CN2010102552573A patent/CN101899726B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643193A (en) * | 2002-05-22 | 2005-07-20 | 昭和电工株式会社 | Process for producing vapor-grown carbon fibers |
| CN1995503A (en) * | 2006-01-06 | 2007-07-11 | 北京化工大学 | Method for preparing spiral nano carbon fiber |
| CN101384358A (en) * | 2006-02-16 | 2009-03-11 | 拜尔材料科学股份公司 | Continuous preparation method of catalyst |
| CN101314129A (en) * | 2008-07-04 | 2008-12-03 | 浙江大学 | Non-carrier yellow brass catalyst for preparing stephanoporate carbon fiber, preparation and process of using |
Non-Patent Citations (1)
| Title |
|---|
| 孙海军等.螺旋纤维的制备与表征.《中国优秀硕士论文全文数据库》.2008,(第12期),16-17、42、44、49. * |
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