CN103276593B - Utilize the method for going fluorine cross-linking reaction to strengthen carbon nano-tube fibre - Google Patents
Utilize the method for going fluorine cross-linking reaction to strengthen carbon nano-tube fibre Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 238000004132 cross linking Methods 0.000 title claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000006115 defluorination reaction Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000003014 reinforcing effect Effects 0.000 claims description 11
- 239000002071 nanotube Substances 0.000 claims description 8
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract 1
- 238000003682 fluorination reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a kind of utilization goes fluorine cross-linking reaction to strengthen the method for carbon nano-tube fibre, comprise: after carbon nano-tube fibre is fluoridized, again in going fully to flood in fluorine reaction solution, until complete fluorine reaction, described in go fluorine reaction solution to comprise electron donor reagent and organic solvent; Or, after being fluoridized by carbon nano-tube fibre, be more fully aided with UV-irradiation in dipping in organic solvent, until complete fluorine reaction, then improve the mechanical property of carbon nano-tube fibre entirety.In the present invention, owing to going can to introduce covalent bonds between CNT and carbon nano tube surface in fluorine course of reaction, namely improve the adhesion between carbon nanotube interface, thus play the effect of fortifying fibre.Present invention process is succinct, with low cost, is easy to scale and implements, and without the need to introducing other reinforcing materials, fully can retain the character of carbon nano-tube fibre self.
Description
Technical Field
The invention relates to a preparation method of a reinforced carbon nanotube fiber, in particular to a method for reinforcing the carbon nanotube fiber by using a defluorination crosslinking reaction, belonging to the field of nano materials.
Background
The carbon nano tube is widely concerned since discovered in 1991, and has the quasi-one-dimensional structural characteristic of being formed by taking a carbon atom hexagonal net surface as a unit, so that the Young modulus of the carbon nano tube is as high as 1TPa, the tensile strength of the carbon nano tube exceeds 100GPa, the breaking elongation of the carbon nano tube reaches 15% -30%, and the carbon nano tube is far more than that of a common fiber material. In addition, the carbon nano tube has huge application potential in many aspects due to extremely high thermal conductivity, excellent electrical characteristics, good chemical stability, high specific surface area and the like. However, in order to fully utilize the excellent properties of carbon nanotubes, they must be assembled into macroscopic structures such as fibers, ribbons, films, etc. At present, carbon nanotube fibers are becoming a very active research direction, and composite materials prepared by using the carbon nanotube fibers as a matrix or a reinforcement body show application potential in the fields of aerospace, bulletproof equipment, sports equipment and the like.
The commonly used preparation methods of the carbon nanotube fiber mainly comprise a dry spinning method, a direct spinning method and a wet spinning method. These processes all produce fibers with the following disadvantages: the carbon nanotubes have smooth surfaces, and the interfaces between the carbon nanotubes are not combined by chemical bonds, so that the carbon nanotubes are easy to slip, and the mechanical property of the carbon nanotube fiber cannot reach the ideal property. How to improve the interface action of the carbon nano tube so as to enhance the mechanical property of the fiber is a key problem of really putting the carbon nano tube into engineering application.
At present, the method for reinforcing carbon nanotube fibers reported in the literature mainly comprises two parts. One is to combine the fibers with other materials to make composites, including composites with polymers or inorganic bodies, etc. The method needs to perform functional modification on the carbon nano tube, the structure of the carbon nano tube is easy to destroy, the mechanical property enhancement is limited, and the research and development and preparation investment of organic or inorganic bodies compounded with the fiber also restrict the application of the fiber. Another approach is to improve the post-treatment process of the fibers, including twisting, or surface tension driven densification of the fibers, and to improve the carbon material properties using traditional high temperature heat treatment processes, among others. For example, the strength of the carbon nanotube fiber prepared by the dry spinning method still has great deviation from the theoretical strength, which is mainly related to the defects of a large amount of pore structures and the like existing in the fiber, and the mechanical property of the carbon nanotube fiber can be obviously improved by twisting. For another example, passing carbon nanotube fibers through droplets of ethanol can reduce the thickness of the fibers by several orders of magnitude, densify them and thereby improve mechanical properties. However, the above method is simple to operate, but only improves the physical form of the fiber, so that the performance enhancement is limited.
Disclosure of Invention
The invention aims to provide a method for reinforcing carbon nanotube fibers by using a defluorination crosslinking reaction, which realizes the reinforcement of the fibers by using a crosslinking structure between a carbon tube and a carbon tube generated by removing fluorine elements on the surface of a fluorinated carbon nanotube so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of reinforcing carbon nanotube fibers using a defluorination crosslinking reaction comprising:
fully soaking the carbon fluoride nanotube fiber in a defluorination reaction solution until the defluorination reaction is completed, wherein the defluorination reaction solution comprises an electron donor reagent and an organic solvent; or,
fully soaking the carbon fluoride nanotube fiber in an organic solvent and assisting with ultraviolet irradiation until the defluorination reaction is finished.
As one of the preferable embodiments, the preparation process of the fluorinated carbon nanotube fiber comprises: and (2) placing the carbon nano tube fiber in a reaction atmosphere containing fluorine gas to react for more than 5min under the condition that the temperature is higher than or equal to 25 ℃, so as to obtain a target product.
As one of the preferable embodiments, the preparation process of the fluorinated carbon nanotube fiber comprises: under the condition of the temperature of 25-500 ℃, the carbon nano tube fiber is placed in the reaction atmosphere mainly composed of fluorine gas and inert gas to react for 5-600 min, and the target product is obtained.
Preferably, the reaction atmosphere contains fluorine gas and inert gas in a volume ratio of 1: 1.
The inert gas may include, but is not limited to, nitrogen, argon or helium, and the like.
As one of the more preferable embodiments, the defluorination reaction solution contains 0.01 wt% to 5 wt% of the electron donor reagent.
The electron donor reagent may include, but is not limited to, N-dimethyl-p-phenylenediamine or tetrathiafulvalene, and the like.
The organic solvent may include, but is not limited to, ethanol, acetone, tetrahydrofuran, pyrrolidone, N-dimethylformamide, or the like
As one of the more preferable embodiments, the method comprises: and soaking the carbon fluoride nanotube fiber in a defluorination reaction solution for 1-30 min, taking out, and drying to obtain the enhanced carbon nanotube fiber.
As one of the more preferable embodiments, the method comprises: and (3) soaking the carbon fluoride nanotube fiber in an organic solvent, taking out after 1-30 min, and drying to obtain the reinforced carbon nanotube fiber. And irradiating the carbon nano tube fiber for 5-60 min by using ultraviolet light with the wavelength of 200-400 nm and the power of 5-100 milliwatts to obtain the reinforced carbon nano tube fiber.
In a more specific embodiment, the ultraviolet light may have a wavelength of 280nm and a power of 5 mw.
As one of the more preferable embodiments, the method comprises: the traction device drives the carbon fluoride nanotube fiber to pass through the defluorination reaction solution or the organic solvent and obtain full infiltration.
Compared with the prior art, the invention has at least the following advantages:
the tensile strength of the carbon nano tube fiber (hereinafter referred to as fiber) obtained by the treatment of the invention is greatly improved, compared with untreated fiber, the strength can be improved to about 160 percent of the original tensile strength, and meanwhile, the comprehensive mechanical property is also improved;
although the fiber needs to be fluorinated firstly, the subsequent defluorination reaction can remove fluorine without causing obvious damage to the shape of the fiber, and the shape and other properties of the fiber can be still preserved;
thirdly, other reinforcing materials are not introduced in the method, and the finally obtained fiber sample still only consists of the carbon nano tube, so that the original characteristics of high specific surface area and low density are still kept compared with the composite material;
the invention does not need to develop other reinforcing materials and complicated chemical modification, only needs to treat the solution after the fiber is fluorinated in the tubular furnace, has simple equipment and easy operation, and is suitable for large-scale industrial application.
Drawings
Fig. 1 is an infrared spectrum of the carbon nanotube fiber after fluorination and defluorination in example 1 of the present invention, wherein it is shown that the fluorinated carbon nanotube fiber has a very significant characteristic peak of C-F chemical bond, which indicates that the carbon nanotube fiber after fluorination successfully accesses fluorine, and the intensity of the C-F peak after defluorination crosslinking is sharply reduced, and the fluorine is almost disappeared, which indicates that the fluorination and defluorination reactions are successfully performed.
Fig. 2A and 2B are scanning electron micrographs of the carbon nanotube fiber after fluorination and defluorination crosslinking in example 1 of the present invention, respectively, and it can be seen that the diameter of the carbon nanotube fiber after defluorination treatment is reduced, and the appearance structure has not been significantly damaged and changed, and the complete fiber structure is still maintained.
FIG. 3 is a graph showing the tensile strength of the carbon nanotube fibers after fluorination and defluorination crosslinking in example 1 of the present invention, and shows the mechanical properties of the original carbon nanotube fibers (i.e., the original fibers in the figure) and the resulting reinforcing fibers (i.e., the fibers after defluorination by the first method in the figure), and it can be seen that the tensile strength of the reinforcing-treated carbon nanotube fibers is significantly improved compared to the tensile strength of the original fibers and the fibers treated with only an organic solvent (i.e., the fibers treated with only a solvent in the figure).
Detailed Description
As described above, in view of the shortcomings of the prior art, the present invention is directed to a novel method for reinforcing carbon nanotube fibers, which comprises: the carbon nanotube fiber is reinforced by a cross-linked structure between carbon tubes generated in the fluorine removal process by fluorinating the surface of the carbon nanotube and then removing fluorine by chemical reaction.
In a preferred embodiment of the present invention, the method may first utilize a gas mixture containing fluorine as a fluorinating agent, and directly perform a fluorination reaction with the carbon nanotube fiber at a certain temperature and pressure;
the fluorinated fibers may then be defluorinated with an organic solution (e.g., ethanol) containing an electron donor reagent (e.g., N-dimethyl-p-phenylenediamine) or the fibers may also be irradiated with an ultraviolet lamp; after fluorine reaction, the mechanical property of the whole carbon nano tube fiber can be improved.
In the invention, because covalent bond bonding can be introduced between the carbon nano tube and the surface of the carbon nano tube in the defluorination reaction process, the bonding force between the carbon nano tube interfaces is improved, thereby playing the role of reinforcing the fiber.
The method is simple and effective, does not need to introduce other reinforcing materials, and can fully retain the self properties of the carbon nanotube fiber.
The technical solution of the present invention is further described below with reference to several preferred embodiments. It should be understood that these examples are only for illustrating the present invention, and are not to be construed as limiting the scope of the present invention.
Example 1 this example relates to a process for enhancing carbon nanotube fibers by solution dip defluorination crosslinking comprising the steps of:
(1) carrying out fluorination treatment on the carbon nanotube fiber at high temperature: fixing a section of carbon nanotube fiber on a copper-nickel alloy reaction boat, placing the reaction boat in a tubular reaction furnace, setting the temperature at 150 ℃, vacuumizing the reaction tube to 10-20 Pa, stopping vacuumizing, and introducing mixed gas of fluorine gas and nitrogen gas which are uniformly mixed in advance, wherein the mixing volume ratio is 1: 10, the gas flow is 50ppm, and the reaction time is 10 min.
(2) Preparing a defluorination reaction solution: fully dissolving a solute, namely N, N-dimethyl-p-phenylenediamine, in ethanol, wherein the mass concentration of the solute in the solution is 0.5 wt%;
(3) carrying out defluorination crosslinking treatment on the fluorinated fiber: and (3) putting the fluorinated fiber in the prepared solution, taking out after 2 minutes, and drying to obtain the reinforced carbon nanotube fiber.
Example 2 this example relates to a process for defluorination crosslinking by ultraviolet irradiation to enhance carbon nanotube fibers comprising the steps of:
(1) carrying out fluorination treatment on the carbon nanotube fiber at high temperature: fixing a section of carbon nanotube fiber on a copper-nickel alloy reaction boat, placing the reaction boat in a tubular reaction furnace, setting the temperature at 150 ℃, vacuumizing the reaction tube to 10-20 Pa, stopping vacuumizing, and introducing mixed gas of fluorine gas and nitrogen gas which are uniformly mixed in advance, wherein the mixing volume ratio is 1: 10, the gas flow is 50ppm, and the reaction time is 10 min.
(2) Carrying out defluorination crosslinking treatment on the fluorinated fiber: soaking the fluorinated fiber in an ethanol solvent, irradiating for 25 minutes by using an ultraviolet lamp with the wavelength of 280nm, wherein the power of the ultraviolet lamp is 5 milliwatts, taking out and drying to obtain the reinforced carbon nanotube fiber.
It should be noted that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A method for reinforcing carbon nanotube fibers using a defluorination crosslinking reaction, comprising:
fully soaking the carbon fluoride nanotube fiber in a defluorination reaction solution for 1-30 min, then taking out, completing the defluorination reaction, taking out and drying to obtain the reinforced carbon nanotube fiber, wherein the defluorination reaction solution contains 0.01-5 wt% of an electron donor reagent and an organic solvent, and the electron donor reagent comprises N, N-dimethyl-p-phenylenediamine or tetrathiafulvalene; or,
fully soaking the carbon fluoride nanotube fiber in an organic solvent, irradiating for 5-60 min by using ultraviolet light with the wavelength of 200-400 nm and the power of 5-100 milliwatts to complete defluorination reaction, and taking out and drying to obtain the reinforced carbon nanotube fiber;
the organic solvent comprises ethanol, acetone, tetrahydrofuran, pyrrolidone or N, N-dimethylformamide.
2. The method of claim 1, wherein the fluorinated carbon nanotube fiber is prepared by a process comprising: and (2) placing the carbon nano tube fiber in a reaction atmosphere containing fluorine gas to react for more than 5min under the condition that the temperature is higher than or equal to 25 ℃, so as to obtain a target product.
3. The method of claim 2, wherein the fluorinated carbon nanotube fiber is prepared by a process comprising: under the condition of the temperature of 25-500 ℃, the carbon nano tube fiber is placed in the reaction atmosphere mainly composed of fluorine gas and inert gas to react for 5-600 min, and the target product is obtained.
4. The method of claim 2 or 3, wherein the reaction atmosphere comprises fluorine gas and inert gas in a volume ratio of 1: 1.
5. The method for reinforcing carbon nanotube fiber using defluorination crosslinking reaction as set forth in claim 2 or 3, wherein said inert gas comprises nitrogen, argon or helium.
6. The method of claim 1 for reinforcing carbon nanotube fibers using defluorination crosslinking reaction, comprising: the traction device drives the carbon fluoride nanotube fiber to pass through the defluorination reaction solution or the organic solvent and obtain full infiltration.
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| US11155465B2 (en) | 2015-04-22 | 2021-10-26 | Stella Chemifa Corporation | Cross-linked structure of carbon material and method for producing same |
| US11220433B2 (en) * | 2015-06-23 | 2022-01-11 | Indiana University Research And Technology Corporation | Process for modification of carbon surfaces |
| CN106592215B (en) * | 2016-12-19 | 2018-11-02 | 曲阜师范大学 | A method of preparing fluorine content and size adjustable fluorinated carbon fiber |
| CN108928809A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | The fluorine carbon ratio of carbon fluoride nano-tube regulates and controls method |
| CN107163912B (en) * | 2017-06-13 | 2019-08-20 | 四川大学 | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material |
| CN109411752A (en) * | 2017-08-15 | 2019-03-01 | 天津大学 | A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas |
| CN109599535B (en) * | 2017-09-30 | 2021-06-04 | 天津大学 | Fluorinated carbon nanotube/carbon nanotube sponge composite material for lithium-sulfur battery anode and preparation method thereof |
| CN109295550B (en) * | 2018-09-21 | 2021-02-02 | 武汉大学苏州研究院 | Carbon nanotube fiber material with high strength, high elastic modulus and excellent ductility and preparation method thereof |
| CN109231184A (en) * | 2018-11-13 | 2019-01-18 | 广州百思创科技有限公司 | A kind of multi-functional conductive carbon nanotube and its preparation method and application |
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| JPH04175266A (en) * | 1990-11-07 | 1992-06-23 | Nobuatsu Watanabe | Carbon fiber reinforced carbon composite material |
| CN101177260A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Method for preparing primary amine carbon nano tube |
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