CN100500959C - Method for preparing spiral nano carbon fiber - Google Patents
Method for preparing spiral nano carbon fiber Download PDFInfo
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- CN100500959C CN100500959C CNB2006100001654A CN200610000165A CN100500959C CN 100500959 C CN100500959 C CN 100500959C CN B2006100001654 A CNB2006100001654 A CN B2006100001654A CN 200610000165 A CN200610000165 A CN 200610000165A CN 100500959 C CN100500959 C CN 100500959C
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Abstract
The invention relates to a spiral nanometer carbon fiber, in detail the manufacturing method of spiral nanometer carbon fiber. In the invention the acetylene is carbon source, the hydrogen is carrier gas, the nitrogen or argon gas is diluent air, the nickel plate is catalyst, the PCl3 is cocatalyst. The spiral nanometer carbon fiber is produced by CVD in lower temperature. The invention is provided with simple method and process, easy control, low cost, high output and purity, and convenience industrial production. Prepared spiral nanometer carbon fiber is provided with wide application prospect in strengthening structure, absorbing material and microelectronic device so on.
Description
Technical field
The present invention relates to spiral nano carbon fiber, specifically a kind of method for preparing spiral nano carbon fiber.
Background technology
Helical carbon fiber is a kind of functional form carbon fiber, can make by the solid phase carbonization of macromolecule organic fiber or the gas phase catalysis pyrolysis growth of low molecular hydrocarbons, heat resistance with general carbon fiber, chemical stability, the electric heating conductibility, thermal expansivity is low, rub resistance, it is low to wear and tear, density is low, give birth to the body compatibility and wait excellent properties well, its special spiral has then given material typical hand intrinsic characteristics, better elastic, good combination with matrix, be expected to as novel radio-radar absorber, little responsive energy absorber, stealth material, micromechanical components such as Microspring etc. strengthen in structure, absorbing material, electromagnetic shielding material, fields such as microelectronic component have broad application prospects.
At present about the preparation of helical carbon fiber both at home and abroad report two kinds of chemical vapour deposition technique and pitch melt spinning methods are arranged, chemical vapour deposition technique (CVD) is generally adopted in the preparation of spiral nano carbon fiber, with the lower carbon number hydrocarbons compound is carbon source, nanometer Fe, Cr, Ni, Cu and Nanoalloy particle thereof are catalyst, the preparation spiral nano carbon fiber, the preparation technology of above-mentioned nanocatalyst is very complicated, and particle diameter is restive, general passing through Fe, Cr, Ni, the salting liquid of metals such as Cu is adsorbed on the surface of particles such as superfine silicon dioxide, prepare the metallic catalyst that is attached to particle surfaces such as superfine silicon dioxide by hydrogen reducing again, these superfine silicon dioxide particles can be mingled in the middle of the spiral nano carbon fiber, are difficult to remove clean.It is generally acknowledged the internal diameter and the catalyst granules equal diameters of carbon fiber and CNT (carbon nano-tube), people always try every possible means to obtain the less catalyst of particle diameter, and minor diameter Preparation of catalysts difficulty big, cost an arm and a leg, its application is subjected to certain restriction.
Summary of the invention
The objective of the invention is to disclose the new method that a kind of technology is simple, the high and low cost of output prepares spiral nano carbon fiber, to satisfy the needs of relevant field development.
To achieve these goals, technical scheme of the present invention is: a kind of method for preparing spiral nano carbon fiber 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 by chemical vapour deposition technique; Described reaction temperature is 550 ℃ one 700 ℃; Diluent gas nitrogen or argon gas are 2～5:1 with the ratio of acetylene flow; Hydrogen is 3～5:1 with the ratio of acetylene flow; PCl
3The flow of co-catalyst is 0.02～0.05ml/min; The thickness of catalyst nickel plate is 0.1～2mm, and nickel plate catalyst will carry out Surface Nanocrystalline before reaction, and the high speed blasting treatment was carried out 30 minutes in nickel plate surface, soaks in watery hydrochloric acid or dilute sulfuric acid 5～10 hours then, and use dry back.
Described nickel plate catalyst is reused, and the remaining nickel plate of last secondary response catalyst soaked in watery hydrochloric acid or dilute sulfuric acid 5～10 hours through sand papering, and dry back is reused.
Described nickel plate levels of catalysts or vertically be placed on above the graphite cake.
When described nickel plate catalyst was placed perpendicular to graphite cake, all there was the spiral nano carbon fiber growth both sides of nickel plate catalyst, and productive rate doubles than horizontal positioned.
With traditional chemical vapour deposition technique prepare spiral nano carbon fiber to catalyst require height and complex process, cost is higher compares, the present invention has following beneficial effect, and method provided by the invention is simple to operation, the product purity height, the specific yield height is beneficial to generation in enormous quantities.Have broad application prospects in fields such as structure enhancing, absorbing material, electromagnetic shielding material, microelectronic components.
Description of drawings
Fig. 1 is the stereoscan photograph of the spiral nano carbon fiber of embodiment 1 preparation.
Fig. 2 is the stereoscan photograph of the spiral nano carbon fiber of embodiment 2 preparations.
Fig. 3 is the stereoscan photograph of the spiral nano carbon fiber of embodiment 3 preparations.
Fig. 4 is the stereoscan photograph of the spiral nano carbon fiber of embodiment 4 preparations.
The specific embodiment
Embodiment 1
Be that the nickel plate catalyst that 1mm, length and width are respectively 150mm and 30mm carries out surface treatment with thickness before the reaction, the high speed blasting treatment was carried out 30 minutes in nickel plate surface, soaked 5 hours in watery hydrochloric acid then, be placed on the flat-temperature zone of tube furnace after the drying, nickel plate levels of catalysts is placed on the graphite cake; Reaction system is vacuumized, with nitrogen replacement three times, feed nitrogen, the flow of nitrogen is 200ml/min, is warmed up to 650 ℃ under nitrogen atmosphere, is that carrier gas adds PCl with hydrogen when feeding acetylene
3Co-catalyst, PCl
3The flow of co-catalyst is 0.03ml/min, diluent gas nitrogen is that (wherein: acetylene is 40ml/min to 2.5:1 with the ratio of acetylene flow, nitrogen is 100ml/min), hydrogen is that (wherein: acetylene is 40ml/min to 3:1 with the ratio of acetylene flow, hydrogen is 120ml/min), the reaction constant temperature time is 35min, carries out the catalyse pyrolysis reaction; Reaction finishes the back and naturally cool to room temperature under nitrogen atmosphere, can obtain the spiral nano carbon fiber (referring to Fig. 1) of 1.7361g.
Embodiment 2
Be that the nickel plate catalyst that 1.5mm, length and width are respectively 150mm and 30mm carries out surface treatment with thickness before the reaction, the high speed blasting treatment was carried out 30 minutes in nickel plate surface, in dilute sulfuric acid, soaked 8 hours then, be placed on the flat-temperature zone of tube furnace after the drying, nickel plate catalyst vertically is placed on the graphite cake of level; Reaction system is vacuumized, with argon replaces three times, feed argon gas, the flow of argon gas is 200ml/min, is warmed up to 670 ℃ under argon gas atmosphere, is that carrier gas adds PCl with hydrogen when feeding acetylene
3Co-catalyst, PCl
3The flow of co-catalyst is 0.04ml/min, the diluent gas argon gas is that (wherein: acetylene is 50ml/min to 2:1 with the ratio of acetylene flow, argon gas is 100ml/min), hydrogen is that (wherein: acetylene is 50ml/min to 3.5:1 with the ratio of acetylene flow, hydrogen is 175ml/min), the reaction constant temperature time is 40min, carries out the catalyse pyrolysis reaction, reaction finishes the back and naturally cool to room temperature under argon gas atmosphere, can obtain the spiral nano carbon fiber (referring to Fig. 2) of 3.5371g.
Embodiment 3
Be that the nickel plate catalyst that 0.5mm, length and width are respectively 150mm and 30mm carries out surface treatment with thickness before the reaction, the high speed blasting treatment was carried out 30 minutes in nickel plate surface, soaked 5 hours in watery hydrochloric acid then, be placed on the flat-temperature zone of tube furnace after the drying, nickel plate levels of catalysts is placed on the graphite cake; Reaction system is vacuumized, with nitrogen replacement three times, feed nitrogen, the flow of nitrogen is 200ml/min, is warmed up to 680 ℃ under nitrogen atmosphere, is that carrier gas adds PCl with hydrogen when feeding acetylene
3Co-catalyst, PCl
3The flow of co-catalyst is 0.05ml/min, diluent gas nitrogen is that (wherein: acetylene is 45ml/min to 3:1 with the ratio of acetylene flow, nitrogen is 135ml/min), hydrogen is that (wherein: acetylene is 45ml/min to 4:1 with the ratio of acetylene flow, hydrogen is 180ml/min), the reaction constant temperature time is 60min, carries out the catalyse pyrolysis reaction, reaction finishes the back and naturally cool to room temperature under nitrogen atmosphere, can obtain the spiral nano carbon fiber (referring to Fig. 3) of 2.1845g.
Embodiment 4
Be that the nickel plate catalyst that 2mm, length and width are respectively 150mm and 30mm carries out surface treatment with thickness before the reaction, the high speed blasting treatment was carried out 30 minutes in nickel plate surface, in dilute sulfuric acid, soaked 10 hours then, be placed on the flat-temperature zone of tube furnace after the drying, nickel plate catalyst vertically is placed on the graphite cake of level; Reaction system is vacuumized, with argon replaces three times, feed argon gas, the flow of argon gas is 200ml/min, is warmed up to 700 ℃ under argon gas atmosphere, is that carrier gas adds PCl with hydrogen when feeding acetylene
3Co-catalyst, PCl
3The flow of co-catalyst is 0.04ml/min, the diluent gas argon gas is that (wherein: acetylene is 50ml/min to 3:1 with the ratio of acetylene flow, argon gas is 150ml/min), hydrogen is that (wherein: acetylene is 50ml/min to 3:1 with the ratio of acetylene flow, hydrogen is 150ml/min), the reaction constant temperature time is 60min, carries out the catalyse pyrolysis reaction, reaction finishes the back and naturally cool to room temperature under argon gas atmosphere, can obtain the spiral nano carbon fiber (referring to Fig. 4) of 3.9531g.
Claims (3)
1. method for preparing spiral nano carbon fiber, it 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 by chemical vapour deposition technique; Described reaction temperature is 550 ℃-700 ℃; Diluent gas nitrogen or argon gas are 2～5:1 with the ratio of acetylene flow; Hydrogen is 3～5:1 with the ratio of acetylene flow; PCl
3The flow of co-catalyst is 0.02～0.05ml/min; The thickness of catalyst nickel plate is 0.1～2mm, and nickel plate catalyst will carry out Surface Nanocrystalline before reaction, and the high speed blasting treatment was carried out 30 minutes in nickel plate surface, soaks in watery hydrochloric acid or dilute sulfuric acid 5～10 hours then, and use dry back.
2. the method for preparing spiral nano carbon fiber according to claim 1, it is characterized in that: described nickel plate catalyst is reused, the remaining nickel plate of last secondary response catalyst soaked in watery hydrochloric acid or dilute sulfuric acid 5～10 hours through sand papering, and dry back is reused.
3. prepare the method for spiral nano carbon fiber according to claim 1, it is characterized in that: described nickel plate levels of catalysts or vertically be placed on above the graphite cake.
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| CN100500959C true CN100500959C (en) | 2009-06-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101245502B (en) * | 2008-03-19 | 2010-06-23 | 北京化工大学 | Method for producing cochleiform carbon fiber with catalyst |
| CN101899726B (en) * | 2010-08-17 | 2012-05-23 | 西南交通大学 | Method for preparing nano-carbon fibers |
| CN103710649B (en) * | 2014-01-16 | 2015-08-19 | 昌吉市银杏新材料科技有限公司 | A kind of fibre reinforced titanium alloy composite material and preparation method thereof |
| CN107698937A (en) * | 2017-09-08 | 2018-02-16 | 常熟市瑞思知识产权服务有限公司 | A kind of helical spring composite and preparation method thereof |
| CN108998861B (en) * | 2018-06-08 | 2020-09-01 | 四川理工学院 | Preparation method of spiral carbon nanofiber |
| CN108624992B (en) * | 2018-06-08 | 2020-10-09 | 四川理工学院 | Spiral nano carbon fiber and preparation method thereof |
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