CN101338458B - Heat treatment process of PBO/single-wall carbon nanotube composite fiber - Google Patents
Heat treatment process of PBO/single-wall carbon nanotube composite fiber Download PDFInfo
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- CN101338458B CN101338458B CN2008101368867A CN200810136886A CN101338458B CN 101338458 B CN101338458 B CN 101338458B CN 2008101368867 A CN2008101368867 A CN 2008101368867A CN 200810136886 A CN200810136886 A CN 200810136886A CN 101338458 B CN101338458 B CN 101338458B
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- walled carbon
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Abstract
A heat treatment method of the composite fiber of a PBO/single-walled carbon nano-tube relates to the heat treatment method of the composite fiber. The heat treatment method solves the problem of the imperfect microcrystalline structure of the composite fiber of the PBO/single-walled carbon nano-tube. The method is as follows: the composite fiber of the PBO/single-walled carbon nano-tube is put into a high temperature ceramic tube that is 10mm to 20mm in diameter and 0.6m to 1.2m in length; and the composite fiber of the PBO/single-walled carbon nano-tube is processed for 1s to 10mm under the protection of Nitrogen and on conditions that the power of resistance wire winded around the outer part of the high temperature ceramic tube is 500W to 2000W; the voltage of a transformer is less than 220V ; the inner temperature of the high temperature ceramic tube ranges from room temperature to the temperature of 800 DEG C, and the fiber tension of the PBO/single-walled carbon nano-tube is less than 10g/d. A Fig 1 shows that the diffraction peak intensity of a crystal surface (200) is getting more and more penetrating, which means that the composite material of the PBO/single-walled carbon nano-tube forms the complete microcrystalline structure after being processed by heat treatment.
Description
Technical field
The present invention relates to a kind of heat treatment method of composite fibre.
Background technology
With 4,6-diamino resorcin hydrochlorate (DADHB) and terephthalic acid (TPA) (PTA) are polymerization single polymerization monomer, polycondensation can get liquid crystal PBO (Poly-p-phenylene-benzobisthiazole) polymer in polyphosphoric acids, adopt dried spray-wet spinning technology can make pbo fiber, structural formula is as follows:
Pbo fiber is the abbreviation of polyparaphenylene's benzo-dioxazole fiber (Poly-p-phenylene-benzobisthiazole), is to contain the most rising in the polyamide family of a heteroaromatic member, is the present the highest industrial fiber of intensity in the world.Its TENSILE STRENGTH reaches 5.8GPa, and stretch modulus is 280～380GPa, and heat decomposition temperature is up to 650 ℃, and density only is 1.56 * 10
3Kg/m
3
Single Walled Carbon Nanotube (Single-walled nanotubes, SWNT) thisly curl and the CNT that forms is the graphite that continues by graphite flake layer, diamond, the carbon of another simple substance form of finding after the fullerene, U.S. carbon nanotube technology company (Carbon Nanotechnologies Inc.C-NI) adds 10wt% Single Walled Carbon Nanotube (SWNT) and makes the PBO/SWNT composite fibre in PBO, through experimental study, this composite fibre is two times of pure PBO to the absorbent properties of energy, its TENSILE STRENGTH can reach more than the 8GPa, its combination property has surpassed pbo fiber, causes widely and pays close attention to.
Prepare the PBO/SWNT composite fibre, what at first will solve is exactly the scattering problem of SWNT in the PBO matrix.Because the surface area of SWNT is very big, the surface energy height, therefore, the SWNT for preparing exists with the form of tube bank basically, and reunites together.The nanotube bundle of reuniting can not be given full play to the humidification of SWNT to the PBO matrix.Be difficult to form complete microstructure in the PBO composite fibre of Single Walled Carbon Nanotube so contain.
Summary of the invention
The objective of the invention is provides a kind of heat treatment method of PBO/ Single Walled Carbon Nanotube composite fibre in order to solve the incomplete problem of PBO/ Single Walled Carbon Nanotube composite fibre microstructure.
The heat treatment method of PBO/ Single Walled Carbon Nanotube composite fibre of the present invention is as follows: it is that 10mm～20mm, length are the refractory ceramics pipe of 0.6m～1.2m that PBO/ Single Walled Carbon Nanotube composite fibre is put into diameter, is that 500W～2000W, transformer voltage are that room temperature to 800 ℃, PBO/ Single Walled Carbon Nanotube composite fibre tension force are handled 1s～10min to PBO/ Single Walled Carbon Nanotube composite fibre under less than the condition of 10g/d less than 220V, refractory ceramics pipe internal temperature at nitrogen protection, the power that is wound in refractory ceramics pipe non-essential resistance silk then.
Refractory ceramics pipe of the present invention is outside with the insulation of asbestos heat-insulation layer; With thermocouple control refractory ceramics pipe temperature inside.
The diffraction peak intensity of (200) crystal face is more and more sharp-pointed as seen from Figure 1, illustrates that PBO/ Single Walled Carbon Nanotube composite fibre has after heat treatment formed complete microstructure.The TENSILE STRENGTH of untreated after tested PBO/ Single Walled Carbon Nanotube composite fibre is 3.2GPa, is 3.7GPa through 300 ℃ of heat treatment after-drawing intensity, is 4.6GPa through 500 ℃ of heat treatment after-drawing intensity, and as seen, after heat treatment its mechanical property improves a lot.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of pbo fiber and the heat treated PBO/ Single Walled Carbon Nanotube composite fibre of process, a is the XRD curve of pbo fiber, b is the XRD curve through the PBO/ Single Walled Carbon Nanotube composite fibre after 500 ℃ of heat treatments, and c is the XRD curve through the PBO/ Single Walled Carbon Nanotube composite fibre after 300 ℃ of heat treatments.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the heat treatment method of PBO/ Single Walled Carbon Nanotube composite fibre is as follows in the present embodiment: it is 10mm～20mm that PBO/ Single Walled Carbon Nanotube composite fibre is put into diameter; length is in the refractory ceramics pipe of 0.6m～1.2m, then in nitrogen protection; the power that is wound in refractory ceramics pipe non-essential resistance silk is 500W～2000W; transformer voltage is less than 220V; refractory ceramics pipe internal temperature is a room temperature to 800 ℃; PBO/ Single Walled Carbon Nanotube composite fibre tension force is less than under the condition of 10g/d PBO/ Single Walled Carbon Nanotube composite fibre being handled 1s～10min.
The preparation method of the PBO/ Single Walled Carbon Nanotube composite fibre in the present embodiment is as follows: one, the PBO/ single-wall carbon nanotube polymer is heated to 160 ℃～200 ℃, be-0.08 in vacuum then～-condition of 0.1MPa under vacuum defoamation 12h～72h, after the deaeration at N
2Under the condition of protection, take the mode of resistance wire heating or high-temperature hot oil heating to make that the temperature of PBO/ single-wall carbon nanotube polymer is 160 ℃～200 ℃ after the deaeration, make spinning solution behind sedimentation 12h～72h then; Two, under temperature is 160 ℃～200 ℃, the condition of spinning pressure less than 30MPa, being 80～800 purpose strainer filterings with spinning solution through 5～10 layers of fineness, is that the spinnerets of 0.15mm～0.8mm obtains the silk that diameter is 0.15mm～0.8mm through the aperture again; Three, at N
2Protection, air-gap length are that 10cm～50cm, draw ratio are that the silk that under 1～150 the condition step 2 is made stretches, then through one group of coagulating bath, be to bathe through washing again under 40 ℃～100 ℃ the condition in temperature, promptly get PBO/ Single Walled Carbon Nanotube composite fibre; Wherein one group of coagulating bath in the step 3 is made of phosphate aqueous solution, and concentration reduces successively, and temperature raises successively, and initial concentration is 60mass%, is 0.1mass% by concentration, and initial temperature is-20 ℃, is 40 ℃ by temperature; Washing in the step 3 is bathed by NaHCO
3Or KHCO
3Being dissolved in the concentration that obtains behind the deionized water constitutes less than the aqueous solution of 10mass%.
The preparation method of PBO/ single-wall carbon nanotube polymer is as follows in the present embodiment: what one, will be used for the PBO polymerization contains the single wall carbon nano-tube monomer compound (applying date: on May 21st, 2008, application number; 200810064550.4 patent name is " preparation method who contains the single wall carbon nano-tube monomer compound who is used for the PBO polymerization ") mix according to 1: 3.2～4.5 mass ratio with polyphosphoric acids, be 1 ℃～80 ℃, N in temperature then
2Stir 12h～72h under the condition of protection and obtain mixed solution; Two, with temperature be 100～120 ℃ P
2O
5Join in the mixed solution of step 1 preparation, then at N
2Be warming up to 140 ℃～160 ℃ reaction 2h～10h under the condition of gas shiled; Three, the product that obtains of step 2 is extruded 1～10 time repeatedly with double screw extruder, promptly gets the PBO/ single-wall carbon nanotube polymer; P in the step 1 polyphosphoric acids wherein
2O
5Content be 82mass%～84.5mass%; P in the step 2
2O
5In 24h, join in the mixed solution of step 1 preparation; P in the step 2
2O
5With the mass ratio of the mixed solution of step 1 preparation be 1.2～1.5: 1; In the step 3 initial temperature of each section of double screw extruder screw rod be 180 ℃, by temperature be 210 ℃, reaction mass time of staying in screw rod is 5min～60min.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that the refractory ceramics pipe is outside with the insulation of asbestos heat-insulation layer.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is with thermocouple control refractory ceramics pipe temperature inside.Other is identical with the specific embodiment one.
Claims (3)
1. the heat treatment method of a PBO/ Single Walled Carbon Nanotube composite fibre; the heat treatment method that it is characterized in that PBO/ Single Walled Carbon Nanotube composite fibre is as follows: it is 10mm～20mm that PBO/ Single Walled Carbon Nanotube composite fibre is put into diameter; length is in the refractory ceramics pipe of 0.6m～1.2m, then in nitrogen protection; the power that is wound in refractory ceramics pipe non-essential resistance silk is 500W～2000W; transformer voltage is less than 220V; refractory ceramics pipe internal temperature is 300 ℃～500 ℃; PBO/ Single Walled Carbon Nanotube composite fibre tension force is less than under the condition of 10g/d PBO/ Single Walled Carbon Nanotube composite fibre being handled 1s～10min.
2. the heat treatment method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that the refractory ceramics pipe is outside with the insulation of asbestos heat-insulation layer.
3. the heat treatment method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that with thermocouple control refractory ceramics pipe temperature inside.
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| CN2008101368867A CN101338458B (en) | 2008-08-08 | 2008-08-08 | Heat treatment process of PBO/single-wall carbon nanotube composite fiber |
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| CN101338458B true CN101338458B (en) | 2010-06-16 |
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| US6852410B2 (en) * | 2002-07-01 | 2005-02-08 | Georgia Tech Research Corporation | Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same |
| US20070009421A1 (en) * | 2004-12-01 | 2007-01-11 | William Marsh Rice University | Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip |
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2008
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| US6852410B2 (en) * | 2002-07-01 | 2005-02-08 | Georgia Tech Research Corporation | Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same |
| US20070009421A1 (en) * | 2004-12-01 | 2007-01-11 | William Marsh Rice University | Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip |
| CN101130431A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院金属研究所 | Method for purifying nano carbon fiber of multi-wall carbon nano-tube |
| CN101139742A (en) * | 2006-09-04 | 2008-03-12 | 中国科学院化学研究所 | Fibre structure of carbon nano tube/nano oxide nano composite material and preparation method and use thereof |
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