CN101723350A - Surface modifying method of carbon nanotube fibers - Google Patents
Surface modifying method of carbon nanotube fibers Download PDFInfo
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- CN101723350A CN101723350A CN200810234754A CN200810234754A CN101723350A CN 101723350 A CN101723350 A CN 101723350A CN 200810234754 A CN200810234754 A CN 200810234754A CN 200810234754 A CN200810234754 A CN 200810234754A CN 101723350 A CN101723350 A CN 101723350A
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Abstract
The invention provides a surface modifying method of carbon nanotube fibers. Fibers are drawn from carbon nanotube arrays into band-shaped carbon nanotube arrays; an organic solution or inorganic solution is introduced before spinning; surface modifying treatment is carried out on the spinning carbon nanotube fibers or spun carbon nanotube fibers by a covalent or non-covalent bonding mode for wet spinning into the carbon nanotube fibers; the carbon nanotube fibers are treated by a solution or solution drop and surface spray coating technique or electrochemical deposition technique so that carbon nanotubes are organized, oriented and aggregated again; certain molecules are introduced on the surfaces of the carbon nanotubes by using a non-covalent method so that the surfaces are modified; and finally, the carbon nanotube fibers have good mechanical strength and electrical performance. The method not only improves the strength of the carbon nanotube fibers, but also enables the carbon nanotube fibers to have multiple functions.
Description
Technical field
The present invention relates to the preparation of carbon nano-tube fibre, relate in particular to a kind of method of carbon nano-tube fibre being carried out surface modification treatment.
Background technology
Scientific research finds that single-root carbon nano-tube has high intensity and elasticity, and its Young's modulus can reach 1.3TPa, and tensile strength can be up to 150GPa, and at high temperature has super deformability and self-reparing capability of moulding.In addition, carbon nanotube also have great length-to-diameter ratio (greater than 1000), extremely light density (less than steel 1/6), can synthetic electrical properties and some essential propertys of graphite material inherent as: high and low temperature resistance is good, erosion resistance surpasses gold, thermal expansivity is little etc., becomes develop at present the lightest, the strongest, nano-fiber material that function is maximum.
When the carbon nanotube with nanoscale is assembled into carbon nano-tube fibre under the macro-scale, some character of material as: the transfer behavior of carrying capacity, electric charge etc. will be inferior to the behavior of single-root carbon nano-tube.This is because the performance of carbon nano-tube fibre, also will depend on interaction between the arranging density of carbon nanotube in fiber, orientation degree, the tube and tube and mode of connection etc. largely except relevant with the textural property of carbon nanotube itself.At present, the preparation method of carbon nano-tube fibre mainly contains: 1) under the effect in external force or outfield, carbon nanotube is scattered in spinning forms in the macromolecule medium; 2) the carbon pipe is dissolved in super acids solution,, reels off raw silk from cocoons into fiber at last in highly concentrated solution because of its protonated must orientation in surface reaches liquid crystal state; 3) direct spinning in the gas phase building-up process: promptly,, can obtain carbon nano-tube film at the tube furnace the other end continuously, make carbon pipe orientation, fine and close film or the fiber of obtaining by tractive as alcohol, ester, ether etc. by ceaselessly adding catalyzer and carbon source; 4) classifying the presoma spinning as with height-oriented carbon nano-pipe array forms.Above-mentioned method 3) and 4) be based on dry technique and prepare the pure nano-carbon tube filamentary material, can avoid the carbon pipe to disperse and the technological difficulties of orientation, and become two kinds of methods quite being paid close attention to.
At present, can realize that the dry-spinning technology is also few in number, more in the mechanical property of paying close attention to carbon nano-tube fibre.Studies show that, by improving the quality of carbon nanotube, prolong the length of carbon nanotube itself, improve the orientation degree of carbon pipe, the ratio tensile strength of carbon nano-tube fibre and specific Young's modulus can obviously be better than existing high-performance engineering carbon fibre material, even exceed about 10 times than optimum carbon fiber T1000.
Carbon nano-tube fibre also can have other function concurrently except having excellent mechanical property.Because carbon nano-tube fibre is made up of a large amount of carbon nanotubes, has big specific surface area and high surface reaction ability; Therefore,, make carbon nano-tube fibre have high-modulus, high-intensity while, also can have functions such as conduction, heat conduction, radioprotective, temperature sensor and humidity, will become a kind of ideal multifunctional nano filamentary material by surface modification and reaction treatment.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of method of carbon nano-tube fibre being carried out surface modification treatment is provided.
Purpose of the present invention is achieved through the following technical solutions:
The surface modifying method of carbon nano-tube fibre, characteristics are: introduced organic solution or inorganic solution before spinning, by bonding mode covalently or non-covalently the carbon nano-tube fibre of carbon nanotube in the spinning or Cheng Sihou is carried out surface modification treatment.
Further, the surface modifying method of above-mentioned carbon nano-tube fibre, the banded carbon nano-pipe array that comes out in wire drawing lists and is coated with machine solution or inorganic solution.
Further, the surface modifying method of above-mentioned carbon nano-tube fibre, banded carbon nano pipe array process organic solution system or inorganic solution system with wire drawing is come out directly are spun to carbon nano-tube fibre in organic solution or inorganic solution.
Further, the surface modifying method of above-mentioned carbon nano-tube fibre, described organic solution system is steam condition system or steam fog state system, described inorganic solution system also is steam condition system or steam fog state system; The banded carbon nano pipe array that wire drawing is soon come out is through the steam condition system of organic solution or the steam fog state system of organic solution, the banded carbon nano pipe array that perhaps wire drawing is come out is through the steam condition system of inorganic solution or the steam fog state system of inorganic solution, is spun to carbon nano-tube fibre in the steam condition system of solution or steam fog state system.
Further, the surface modifying method of above-mentioned carbon nano-tube fibre, the banded carbon nano-pipe array that comes out in wire drawing lists the spraying polymers soln.
Further, the surface modifying method of above-mentioned carbon nano-tube fibre, the banded carbon nano pipe array that wire drawing is come out passes through polymers soln, directly is spun to carbon nano-tube fibre in polymers soln.
Again further, the surface modifying method of above-mentioned carbon nano-tube fibre, the banded carbon nano pipe array that wire drawing is come out soaks into by polymers soln, is spun to carbon nano-tube fibre in the polymers soln fog that spraying forms.
Again further, the surface modifying method of above-mentioned carbon nano-tube fibre, the banded carbon nano pipe array electrochemical deposition that wire drawing is come out, the banded carbon nano pipe array that wire drawing is soon come out is through two ganoid Pt balls, fiber between the two Pt balls passes through electrolytic solution, insert the Pt wire electrode in the electrolytic solution, constitute electrolyzer and carry out the electrochemical deposition reaction.Handle by electrochemical electrolysis, introduce metal plating or oxides coating on the carbon nano-tube fibre surface.
In spinning, spray or wet-spinning or electrochemical deposition by the surface, with organic functions small molecules, inorganic molecule or biomacromolecule covalently or non-covalently method be incorporated in the carbon nano-tube fibre, improve the mechanical strength of carbon nano-tube fibre, simultaneously introduce nano metal particles in carbon nano-tube fibre, quantum dot, biomacromolecule or photoelectricity small molecules make fiber have multifunctionality.
Substantive distinguishing features and obvious improvement that technical solution of the present invention is outstanding are mainly reflected in:
The present invention is on the basis of carbon nano pipe array dry-spinning, before twisting silk, make carbon nanotube reorganize, be orientated, assemble by solution or solution droplets, surperficial spraying technology or electrochemical deposition technique, obtain better orientation, improve spinning quality greatly, make it have excellent mechanical property.Process for modifying surface in the spinning process can not only improve the carbon nano-tube fibre mechanical property, also can make its multifunction; Certain molecule or the group of non-covalent method introducing makes surface modification and finally makes the superior mechanical property of carbon nano-tube fibre and other functional combining on the carbon nano tube surface, realizes multi-functional.This wet-spinning technology is different from existing any wet spinning process, and the carbon nano-tube fibre that is obtained has higher mechanical strength and preferable conductivity.
Description of drawings
Below in conjunction with accompanying drawing technical solution of the present invention is described further:
Fig. 1: wet-spinning surface-modification method synoptic diagram;
Fig. 2: surface spraying method of modifying synoptic diagram;
Fig. 3: the electrochemical deposition surface-modification method in the spinning process
Fig. 4: the carbon nano-tube fibre stress-strain(ed) curve of wet-spinning preparation.
The implication of each Reference numeral sees the following form among the figure:
| Reference numeral | Implication | Reference numeral | Implication | Reference numeral | Implication |
| ??1 | Carbon nano pipe array | ??2 | Carbon nano-tube fibre | ??3 | Dropper |
| ??4 | Shower nozzle | ??5 | The Pt line electrode | ??6 | The Pt ball shaped electrode |
Embodiment
The present invention is based on carbon nanotube and have big specific surface area and high surface reaction ability, in the spinning process of carbon nanotube in conjunction with Wet technique, be about to carbon nano-tube fibre as the wet-spinning technology and make carbon nanotube reorganize, be orientated, assemble, and the certain molecule of non-covalent method introducing makes surface modification and finally makes carbon nano-tube fibre have good mechanics, electricity and other function on carbon nano tube surface by solvent or solution droplets, surperficial spraying technology or electrochemical deposition technique.
Carry out spinning with carbon nano pipe array as raw material, the carbon nanotube favorable orientation can be prepared high-quality carbon nano-tube fibre by the spinning winding.The present invention introduced organic solution or inorganic solution before spinning, optimize the growth quality of carbon nanotube, by bonding mode covalently or non-covalently carbon nanotube in the spinning or Cheng Sihou carbon nano-tube fibre are carried out surface treatment, improve carbon nano-tube fibre intensity on the one hand, under the condition that does not reduce fibre strength, make the carbon nano-tube fibre multifunction on the other hand.Combination by the multiple function of fiber itself or compound with other functional molecular are realized the intellectuality of carbon nano-tube fibre.Following three kinds of modification processing modes are specifically arranged:
1) wet-spinning, promptly in spinning process with carbon nano-tube film or fiber through containing small molecules or macromolecular solution, be dispersed in these functional moleculars in the carbon nano-tube fibre or on the surface in the mode of absorption.As shown in Figure 1: before spinning, on the banded carbon nano pipe array 1 that wire drawing is come out, drip organic solution or inorganic solution by dropper 3, drop preferably is positioned at the position that fried dough twist has just appearred in carbon nano-tube film, carbon nanotube is soaked into fully and bears enough pulling force; After solution is removed, obtain carbon nano tube composite fibre 2 in later stage drying or evaporative process.Utilizing this method can directly introduce target modification molecule has: polymkeric substance, bioprotein etc., or introduce some molecule such as some dye molecules or dna molecular etc. and make the carbon nano-tube fibre functionalisation of surfaces, create the basis for follow-up bonding reaction.As the carbon nanotube of dna modification, it is immersed HAuCl
4Or AgClO
4, obtain layer of even Au or Ag nanoparticle at the carbon tube-surface, it is inserted the aqueous isopropanol of butyl (tetra) titanate, and hydrolysis, obtain TiO
2The coating of nanoparticle.
2) surperficial spraying method: soon small molecules solution or polymers soln are introduced in the spinning process of carbon nanotube in the mode of spraying carbon nano-tube fibre are carried out surface modification.As shown in Figure 2, be painted on the banded carbon nano pipe array 1 that wire drawing comes out by shower nozzle 4 organic solutions or inorganic solution, the dry back of removing of solution evaporation obtains carbon nano tube composite fibre 2.In addition, the banded carbon nano pipe array 1 that also wire drawing can be come out is through the steam condition system of organic solution or the steam fog state system of organic solution, the banded carbon nano pipe array that perhaps wire drawing come out 1 is through the steam condition system of inorganic solution or the steam fog state system of inorganic solution, is spun to carbon nano-tube fibre 2 in the steam condition system of solution or steam fog state system.Because in spinning process, carbon nanotube constantly is pulled and overturns, thereby obtains uniform coating.This method is used for the direct spraying of oxidation, polymkeric substance and the nanoparticle on carbon nano-tube fibre surface.
3) electrochemical deposition method: design electrochemical cell as shown in Figure 3, carbon nano-tube fibre itself is good conductor, with carbon nano-tube fibre array 1 through two ganoid Pt balls 6, form carbon nanotube electrode (Pt ball shaped electrode 6), drip electrolytic solution by the fiber of dropper 3 between two Pt balls, and in electrolytic solution, insert Pt wire electrode (Pt line electrode 5), and constituting electrolyzer, the banded carbon nano pipe array that wire drawing is come out carries out electrochemical deposition.Carbon nano-tube fibre can realize that the successive spinning process carries out electrodeposit reaction to reach the purpose of surface modification.Utilize this method to prepare the carbon nano-tube fibre of polypyrrole or Fe, Ni modification.
Promptly by surface spraying or wet-spinning or electrochemical deposition, with organic functions small molecules, inorganic molecule or biomacromolecule covalently or non-covalently method be incorporated in the carbon nano-tube fibre, except in order to improve the carbon nano-tube fibre mechanical property, also make its multifunction: the capillary force that forms when 1. utilizing solution evaporation makes the further densification of carbon pipe and improves orientation degree; 2. in carbon nano-tube fibre, introduce some small molecules such as amine molecule, polymer molecule such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), Resins, epoxy (epoxy) etc., change carbon tube-surface character, the sliding resistance that increases between the carbon pipe improves fibrous mechanical property; 3. introduce metal nanoparticle,, make fiber have magnetic or shape memory effect when improving the carbon nano-tube fibre conductive capability as nanoparticles such as Au, Ag, Fe, Ni, Ti; 4. introduce oxide compound such as TiO
2Nanoparticle or quantum dot have photochemical catalysis, photoelectricity transformation function; But 5. introduce induced polymer or conducting polymer; As polyacrylic acid hydrogel pH susceptibility is arranged, polydiacetylene has response to temperature, has piezoelectric properties etc. as polypyrrole; 6. introduce biomacromolecule such as enzyme or antibody molecule, organism or environment are optionally detected and monitor.
Be further described below in conjunction with embodiment, but do not limit protection scope of the present invention with this:
Embodiment 1:
At first be prepared into the carbon nano pipe array of length 0.3mm by the chemical vapor deposition (CVD) method, pull into banded carbon nano pipe array from a traction subsequently, twisting silk dropping before or spraying concentration is PVA water and the alcohol mixed solution (volume ratio 1: 1) of 1wt%, soak, and then by spining technology formation carbon nano-tube fibre, concrete operational path is seen Fig. 1.
Fig. 4 has illustrated that the mechanical strength of the carbon nano-tube fibre of acquisition contrasts under the different spinning process conditions.By the carbon nano-tube fibre of dry-spinning preparation, its intensity only has 0.25GPa, strain 1.9%.And obviously strengthen by the carbon nano-tube fibre intensity of wet-spinning preparation of the present invention, through the carbon nano-tube fibre that wet spinning behind the 0.1wt%PVA solution impregnation obtains, its intensity is 0.81GPa, strain 1.8%; The carbon nano-tube fibre of wet spinning preparation behind the 1wt%PVA solution impregnation, its intensity reaches 1.12GPa, strain 2.0%.
Embodiment 2:
The basic technology route is identical with embodiment 1, adopts different solution that carbon nanotube is soaked into processing, the wet spun fibre product has been produced the influence of different mechanics and conductivity.Different solutions as shown in table 1 is handled the carbon nanotube performance comparison that the back wet spinning obtains.
Table 1
| Sample | Fibre diameter (mm) | Tensile strength (GPa) | Strain (%) | Resistance (k Ω) | Length (mm) | Specific conductivity (S/cm) |
| The dry-spinning fiber | ??5.0 | ??0.27 | ??3 | ??44.6 | ??17.6 | ??201 |
| Ethanol | ??3.3 | ??0.58 | ??2.7 | ??54.9 | ??17.6 | ??375 |
| Sample | Fibre diameter (mm) | Tensile strength (GPa) | Strain (%) | Resistance (k Ω) | Length (mm) | Specific conductivity (S/cm) |
| The 1wt%PVA ethanolic soln | ??3.3 | ??0.78 | ??3.3 | ??67.9 | ??19.4 | ??334 |
| Monochloro methane | ??3.3 | ??0.58 | ??3 | ??48.4 | ??17.0 | ??411 |
| 1wt% epoxidation resin chloroformic solution | ??3.3 | ??0.86 | ??3 | ??62.8 | ??11.6 | ??216 |
Can obviously find out, the performance of wet spun fibre is significantly improved than the dry-spinning fiber, the carbon nano-tube fibre of wet spinning had optimum mechanical properties (0.86GPa) after wherein 1wt% epoxidation resin chloroformic solution was handled, and the carbon nano-tube fibre that monochloro methane is handled the back wet spinning has best electric conductivity (216S/cm).
In sum, wet-spinning technology of the present invention is different from existing any wet spinning process, on the basis of carbon nano pipe array dry-spinning, before twisting silk, make carbon nanotube reorganize, be orientated, assemble by solution or solution droplets, surperficial spraying technology or electrochemical deposition technique, obtain better orientation, improve spinning quality greatly, make it have excellent mechanical property.Process for modifying surface in the spinning process can not only improve the carbon nano-tube fibre mechanical property, also can make its multifunction; Certain molecule or the group of non-covalent method introducing makes surface modification and finally makes the superior mechanical property of carbon nano-tube fibre and other functional combining on the carbon nano tube surface, realize multi-functionally, the carbon nano-tube fibre that is obtained has higher mechanical strength and preferable conductivity.The present invention will further promote the research of carbon nano-tube fibre, and provide bigger space for the research and development of novel intelligent filamentary material.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (8)
1. the surface modifying method of carbon nano-tube fibre is characterized in that: introduced organic solution or inorganic solution before spinning, by bonding mode covalently or non-covalently the carbon nano-tube fibre of carbon nanotube in the spinning or Cheng Sihou is carried out surface modification treatment.
2. the surface modifying method of carbon nano-tube fibre according to claim 1 is characterized in that: the banded carbon nano-pipe array that comes out in wire drawing lists and is coated with machine solution or inorganic solution.
3. the surface modifying method of carbon nano-tube fibre according to claim 1, it is characterized in that: banded carbon nano pipe array process organic solution system or inorganic solution system with wire drawing is come out directly are spun to carbon nano-tube fibre in organic solution or inorganic solution.
4. the surface modifying method of carbon nano-tube fibre according to claim 3, it is characterized in that: described organic solution system is steam condition system or steam fog state system, described inorganic solution system also is steam condition system or steam fog state system; The banded carbon nano pipe array that wire drawing is soon come out is through the steam condition system of organic solution or the steam fog state system of organic solution, the banded carbon nano pipe array that perhaps wire drawing is come out is through the steam condition system of inorganic solution or the steam fog state system of inorganic solution, is spun to carbon nano-tube fibre in the steam condition system of solution or steam fog state system.
5. the surface modifying method of carbon nano-tube fibre according to claim 1, it is characterized in that: the banded carbon nano-pipe array that comes out in wire drawing lists the spraying polymers soln.
6. the surface modifying method of carbon nano-tube fibre according to claim 1 is characterized in that: the banded carbon nano pipe array that wire drawing is come out directly is spun to carbon nano-tube fibre by polymers soln in polymers soln.
7. the surface modifying method of carbon nano-tube fibre according to claim 6, it is characterized in that: the banded carbon nano pipe array that wire drawing is come out soaks into by polymers soln, is spun to carbon nano-tube fibre in the polymers soln fog that spraying forms.
8. the surface modifying method of carbon nano-tube fibre according to claim 1, it is characterized in that: the banded carbon nano pipe array electrochemical deposition that wire drawing is come out, the banded carbon nano pipe array that wire drawing is soon come out is through two ganoid Pt balls, fiber between the two Pt balls passes through electrolytic solution, insert the Pt wire electrode in the electrolytic solution, constitute electrolyzer and carry out the electrochemical deposition reaction.
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|---|---|---|---|
| CN2008102347548A CN101723350B (en) | 2008-10-29 | 2008-10-29 | Surface modifying method of carbon nanotube fibers |
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| CN101723350B CN101723350B (en) | 2011-11-16 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| CN102995162A (en) * | 2012-10-15 | 2013-03-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel skin/core-layer composite fiber as well as preparation method and application thereof |
| CN103043653A (en) * | 2013-01-17 | 2013-04-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method and device for preparing metal-nanoparticle functionalized carbon nanotube |
| CN103306132A (en) * | 2012-03-15 | 2013-09-18 | 苏州捷迪纳米科技有限公司 | Carbon nano tube fiber-graphene composite material and preparation method of the same |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100500556C (en) * | 2005-12-16 | 2009-06-17 | 清华大学 | Carbon nano-tube filament and its production |
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