CN102704040B - Preparation method of high strength carbon fibers - Google Patents
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Abstract
A preparation method of the high strength carbon fibers relates to the technical field of preparation of carbon fibers. The preparation method includes controlling oxygen volume concentration of hot oxygen stabilization atmosphere to be 21.8+-1% to prepare the high strength carbon fibers according to the fact that cyclizing degree of hot oxygen stabilization fibers is 82+-5% and aromatization index is 65+-5%. The tensile strength of the carbon fibers can exceed 3.75GPa.
Description
Technical field
The invention belongs to the preparing technical field of carbon fiber, relate to a kind of method of preparing high-strength carbon fiber, especially take stabilization fiber cyclisation degree (η) as 82 ± 5% and aromatization index (AI) be regulation and control foundation as 65 ± 5%, the oxysome volume concentrations of controlling stabilization atmosphere is 21.8 ± 1%, obtain the stabilization fiber of high-quality, thereby make high-strength carbon fibre more than 3.75GPa.
Background technology
The inhomogeneities of fibrous inside radial structure is one of key factor of restriction carbon fiber TENSILE STRENGTH, and the TENSILE STRENGTH cortex that is embodied in carbon fiber is high and core is low.This kind of defect is mainly derived from two stages: the one, and the spinning stage, because the difference of freezing rate radially of fiber and sovent diffusion speed makes precursor form skin-core structure; The 2nd, in the stabilization stage, because fiber double diffusion speed is radially different, cause the degree of oxidation of PAN fibrocortex to be significantly higher than core.Double diffusion in stabilization process, refers to that oxygen is spread by export-oriented fibrous inside from reaction environment and reacts the volatile small molecule that produces from fibrous inside to external diffusion.Along with reaction is carried out, the combination probability of stabilization fiber skin zone and oxygen is far above core, cause the top layer of fiber to form fine and close oxide layer, oxygen in reaction atmosphere enters into the probability that fibrous inside participates in reaction greatly to be reduced, and the fiber radially PAN macromolecular chain extent of reaction is different and further form skin-core structure.Skin-core structure can be delivered to and in carbon fiber, be formed radial structure defect by carbonisation, thereby reduces the mechanical property of carbon fiber.Therefore the skin-core structure that, reduces stabilization fiber is the effective way that improves carbon fiber mechanical property.In stabilization process, oxidation reaction is to cause fiber to form the main factor of skin-core structure radially inhomogeneous of fiber.Therefore the stabilization degree of controlling stabilization fiber is most important, the method of the judgement stabilization fiber degree existing at present concentrates on the mensuration of the density, oxygen content, skin-core structure of stabilization fiber etc., or adopt cyclisation degree, aromatization index simply to weigh stabilization degree, these methods are relatively single, and the validity instructing for technique is worth discussion; Consider that stabilization oxysome volume concentrations is great on oxidation reaction impact, and adopt current method to be difficult to the regulation and control of single oxysome volume concentrations to be difficult to control and realize.Therefore this patent has proposed a kind of method novel, effectively jointly regulate and control stabilization fiber stabilization oxysome volume concentrations by cyclisation degree (η) and aromatization index (AI), corrected forefathers only by the deficiency of cyclisation degree or aromatization index, made up by the blank of cyclisation degree and aromatization index regulation and control stabilization atmosphere.By cyclization level data η and degree of oxidation data AI, come together effectively to weigh the stabilization degree of PAN fiber in stabilization, and by cyclisation degree (η) and two-parameter thermal oxidation stability metallization processes oxygen concentration and other technological parameters of instructing of aromatization index (AI), for obtaining the stabilization fiber of high-quality, provide new basis for estimation and criterion.
Summary of the invention
Object of the present invention is intended to two extents of reaction (cyclization degree and oxidation reaction degree) the comprehensive regulation stabilization oxysome volume concentrations by stabilization fiber, and guide thermal oxidation stability metallization processes, thereby avoid the formation of stabilization fiber sheath cored structure, forefathers have been corrected only by the deficiency of cyclisation degree or aromatization index, made up by the blank of cyclisation degree and aromatization index regulation and control stabilization atmosphere, made to control the requirement that oxysome volume concentrations obtains stabilization fiber by a kind of effective method and prepares high-strength carbon fibre.By determine the visible Fig. 1 of stabilization oxysome volume concentrations by cyclisation degree (η); By aromatization index (AI), determine that stabilization oxysome volume concentrations is shown in Fig. 2.
The invention provides a kind of preparation method of high-strength carbon fiber, it is characterized in that, take stabilization fiber cyclisation degree (η) as 82 ± 5% and aromatization index (AI) be regulation and control foundation as 65 ± 5%, the oxysome volume concentrations of controlling stabilization atmosphere is 21.8 ± 1%, the control method of stabilization process oxygen concentration is incorporated in the preparation process of carbon fiber, prepares high-intensity carbon fiber.
The η of stabilization fiber and AI numerical value adopt respectively infrared spectrum and X-ray diffraction analysis to measure, and stabilization fiber is rubbed as short fiber, dry 72h for 60 ℃, carry out infrared spectrum analysis, obtain infrared signature peak data; Carry out X-ray diffraction analysis, obtain characteristic diffraction peak data.Computing formula is: η=0.29*I
1630/ (0.29*I
1630+ I
2240), AI=I
22.5/ (I
22.5+ I
17).I wherein
1630for 1630cm
-1place-C=N stretching vibration characteristic absorption peak intensity, I
2240for 2240cm
-1place-the characteristic absorption peak intensity of C ≡ N stretching vibration; I
22.5being that fiber (100) crystal face diffraction maximum is located in 2 θ=17 °, is the characteristic diffraction peak of cyano functional group, I
22.5it is the characteristic diffraction peak of the 2 θ=22.5 ° trapezium structure locating to form in fiber.
Under the stabilization condition of 180 ~ 300 ℃, polyacrylonitrile copolymer fibre is carried out to stabilization and follow-up 300 ~ 1600 ℃ of conventional carbonization treatment, obtain TENSILE STRENGTH higher than the carbon fiber of 3.75GPa, under described stabilization condition, a certain temperature spot or a certain temperature range internal control oxygen gas volume concentrations are 21.8 ± 1%.
Above-mentioned PAN copolymer fibre tow can adopt the fiber of dry method, wet method or dry wet method spinning, and fibre bundle can be 1 ~ 320K.In above-mentioned PAN fibre bundle, copolymer, except containing acrylonitrile monemer, also contains one or more polymer monomers: acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylicacidandesters class, acrylamide, methylene succinic acid, the first acid amides of metering system, acrolein, methylacrolein, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone etc.
Epoxy resin, solvent and the gluing of curing agent mixing material for carbon fiber of preparation are cured as after strip, with epoxy resin and curing agent, carry out the preparation of sample, after sample prepares, fibre bundle is carried out to Mechanics Performance Testing.
Effect of the present invention: adopt infrared spectrometer and X-ray diffractometer to analyze the cyclization degree of stabilization fiber and oxidation reaction degree.Result shows, when cyclisation degree (η) be 82 ± 5% and aromatization index (AI) be in 65 ± 5% scopes time, stabilization oxysome volume concentrations is 21.8 ± 1%, the TENSILE STRENGTH of the carbon fiber drawing all can surpass 3.75GPa.By examples prove, thus by cyclisation degree (η) and aromatization index (AI), determine the oxysome volume concentrations of stabilization fiber, and control thermal oxidation stability metallization processes by oxysome volume concentrations.
Accompanying drawing explanation
Fig. 1, determines stabilization oxysome volume concentrations by cyclisation degree (η);
Fig. 2, determines stabilization oxysome volume concentrations by aromatization index (AI).
The specific embodiment
Below in conjunction with example, further illustrate the present invention, but not as to limitation of the present invention.
After obtaining stabilization fiber, carry out infrared analysis and X-ray diffraction analysis, can obtain every numerical value of characteristic peak intensity.
Cyclisation degree (η) and aromatization index (AI) can be obtained according to formula in claims 1, with this, determine stabilization oxysome volume concentrations.
Embodiment 1: selecting the tow of commercially available Britain CourtauldS company wet method spinning is 3k copolymer fibre; its copolymer composition (by weight) is: acrylonitrile 96%, methylene succinic acid 1%, methyl acrylate 3%; equilibrium moisture content 0.67%; in 180 ℃, 210 ℃, 230 ℃, 253 ℃, 273 ℃ five sections of warm areas, carry out stabilization processing; controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21.7%; the time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 10%, obtains stabilization fiber.By stabilization fiber under the protection of nitrogen, low-temperature carbonization at 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+3% degree of draft, apply-3% degree of draft at 1300 ℃ of temperature, high temperature cabonization 2min, obtains carbon fiber.Stabilization is rubbed into short fiber, carry out infrared spectrum analysis and X-ray diffraction analysis.Epoxy resin 618/ acetone/triethylene tetramine for carbon fiber (10:20:1) liquid gluing of preparation is cured as to strip, then according to GB GB3362-82, corresponding carbon fiber sample is carried out to Mechanics Performance Testing.
Embodiment 2: stabilization gradient temperature becomes 180 ℃, 200 ℃, 240 ℃, 260 ℃, 275 ℃; Controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 260 ℃ of warm areas is 20.9%, and the time of staying is respectively 4min, 18min, 15min, 13min, 10min, amounts to 60min; Stabilization draw ratio becomes 12%.PAN copolymer fibre used and other operating procedures are all with example 1.
Embodiment 3: stabilization gradient temperature becomes 180 ℃, 210 ℃, 230 ℃, 250 ℃, 270 ℃; Controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 21%, and the time of staying is respectively 4min, 20min, 15min, 25min, 20min, amounts to 80min; Stabilization draw ratio becomes 13%.PAN copolymer fibre used and other operating procedures are all with example 1.
Embodiment 4: stabilization gradient temperature becomes 180 ℃, 215 ℃, 233 ℃, 253 ℃, 275 ℃; Controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21.5%, and the time of staying is respectively 4min, 20min, 15min, 25min, 20min, amounts to 80min; Stabilization draw ratio becomes 8%.Low-temperature carbonization at 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 2min, 2min, 2min, 2min, amounts to 8min; Apply+3% degree of draft, apply-3% degree of draft at 1300 ℃ of temperature, high temperature cabonization 3min, obtains carbon fiber.PAN copolymer fibre used and other operating procedures are all with example 1.
Embodiment 5: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21.4%, and apply+4% degree of draft of low-temperature carbonization, applies-4% degree of draft at 1300 ℃ of temperature, and high temperature cabonization 5min obtains carbon fiber.PAN copolymer fibre used and other operating procedures are all with example 4.
Embodiment 6: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 22.7%, and PAN copolymer fibre used and other operating procedures are all with example 4.
Embodiment 7: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 22.5%, and PAN copolymer fibre used and other operating procedures are all with example 5.
Embodiment 8: the 6K tow PAN copolymer fibre that adopts the dry wet method spinning of commercially available Jilin Chemical Industry Company synthetic resin plant, the condensate that fiber is used is acrylonitrile: methyl acrylate: α-chloropropene, use amount is respectively 92:6:2 (wt%), equilibrium moisture content is 0.72%, and density is 1.182g/cm
3resistance to, intensity is 5.62CN/dtex, and extension at break is 15.2%.In 180 ℃, 215 ℃, 235 ℃, 250 ℃, 270 ℃ five sections of warm areas, carry out stabilization processing; controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 21.5%; the time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 12%, obtains stabilization fiber.By stabilization fiber under the protection of nitrogen, low-temperature carbonization at 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+4% degree of draft, apply-2% degree of draft at 1300 ℃ of temperature, high temperature cabonization 2min, obtains carbon fiber.Stabilization is rubbed into short fiber, carry out infrared spectrum analysis and X-ray diffraction analysis.Epoxy resin 618/ acetone/triethylene tetramine for carbon fiber (10:20:1) liquid gluing of preparation is cured as to strip, then according to GB GB3362-82, corresponding carbon fiber sample is carried out to Mechanics Performance Testing.
Embodiment 9: in 180 ℃, 210 ℃, 230 ℃, 250 ℃, 270 ℃ five sections of warm areas, carry out stabilization processing; controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 21.6%; the time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 83min; Degree of draft is 14%, obtains stabilization fiber.PAN copolymer fibre used and other operating procedures are all with example 8.
Embodiment 10: in 185 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ five sections of warm areas, carry out stabilization processing; controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 260 ℃ of warm areas is 21.6%; the time of staying is respectively 1min, 15min, 20min, 25min, 20min, amounts to 81min; Degree of draft is 14%, obtains stabilization fiber.PAN copolymer fibre used and other operating procedures are all with example 8.
Embodiment 11: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 21.6%, and stabilization process draw ratio is 8%, obtains stabilization fiber.PAN copolymer fibre used and other operating procedures are all with example 8.
Embodiment 12: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 22.0%, and stabilization process draw ratio is 6%, obtains stabilization fiber.PAN copolymer fibre used and other operating procedures are all with example 10.
Embodiment 13: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 22.2%, and apply+4% degree of draft of low-temperature carbonization, applies-4% degree of draft at 1300 ℃ of temperature, and high temperature cabonization 5min obtains carbon fiber.PAN copolymer fibre used and other operating procedures are all with example 10.
Embodiment 14: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 250 ℃ of warm areas is 22.5%, and PAN copolymer fibre used and other operating procedures are all with example 8.
Embodiment 15: the 12kPAN copolymer fibre that adopts oil of SPC company dry method spinning, the condensate that fiber is used is acrylonitrile: hydroxyalkyl acrylonitrile: metering system benzylacetone, use amount is respectively 93:6:1 (wt%), and equilibrium moisture content is 0.52%, and density is 1.190g/cm
3intensity is 6.62CN/dtex; extension at break is 16.4%; in 180 ℃, 220 ℃, 235 ℃, 255 ℃, 267 ℃ five sections of warm areas, carry out stabilization processing; controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21%; the time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 4%, obtains stabilization fiber.By stabilization fiber under the protection of nitrogen, low-temperature carbonization at 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+5% degree of draft, apply-2% degree of draft at 1300 ℃ of temperature, high temperature cabonization 2min, obtains carbon fiber.Other technological parameters and operating procedure be all with example 1,
Embodiment 16: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 21.1%, and stabilization process draw ratio is 7%, and precursor kind and other technological parameters and operating procedure are all with example 15.
Embodiment 17: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 22.3%, and stabilization process draw ratio is 9%, and precursor kind and other technological parameters and operating procedure are all with example 15.
Embodiment 18: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 21.8%, and stabilization process draw ratio is 11%, and precursor kind and other technological parameters and operating procedure are all with example 15.
Embodiment 19: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 22.7%; by stabilization fiber under the protection of nitrogen; low-temperature carbonization at 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+6% degree of draft, at 1300 ℃ of temperature, apply-4% degree of draft, high temperature cabonization 2min, precursor kind and other technological parameters and operating procedure are all with example 15.
Embodiment 20: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 20.8%, and precursor kind and other technological parameters and operating procedure are all with example 15.
Embodiment 21: controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 255 ℃ of warm areas is 21.8%, and precursor kind and other technological parameters and operating procedure are all with example 19.
Embodiment 22: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, the condensate that fiber is used is acrylonitrile: acrylamide: metering system benzylacetone, use amount is respectively: 92:6:2 (wt%), and equilibrium moisture content is 0.58%, density is 1.193g/cm
3, intensity is 6.02cN/dtex, and extension at break is 17.4%, and controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21.6%, and stabilization draw ratio becomes 3%, and other technological parameters and operating procedure are all with example 1.
Embodiment 23: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and stabilization draw ratio becomes 6%, and other technological parameters and operating procedure are all with example 1.
Embodiment 24: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and stabilization draw ratio becomes 9%, and controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 21.4%, and other technological parameters and operating procedure are all with example 1.
Embodiment 25: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 22.5%, and stabilization draw ratio becomes 12%, and other technological parameters and operating procedure are all with example 1.
Embodiment 26: the 48kPAN copolymer fibre that adopts Japanese Xu Hua company to become to produce, and the condensate that fiber is used is acrylonitrile: allyl chloride: α-chloropropene, use amount is respectively: 92:7:1 (wt%), equilibrium moisture content is 0.69%, density is 1.183g/cm
3, intensity is 6.72cN/dtex, and extension at break is 19.4%, and stabilization draw ratio becomes 12%, and controlling carrier of oxygen volume concentrations in the interior stabilization atmosphere of 253 ℃ of warm areas is 22.6%, other technological parameters and operating procedure are all with example 1.
Embodiment 27: the 48kPAN copolymer fibre that adopts Japanese Xu Hua company to become to produce, and stabilization draw ratio becomes 6%, and other technological parameters and operating procedure are all with example 1.
Embodiment 28: the 48kPAN copolymer fibre that adopts Japanese Xu Hua company to become to produce, and stabilization draw ratio becomes 1%, and other technological parameters and operating procedure are all with example 4.By the cyclisation degree η of the TENSILE STRENGTH of the carbon fiber obtaining under different condition in above-described embodiment and stabilization fiber and aromatization index AI result as table 1.
Table 1: embodiment stabilization fiber and carbon fiber numerical value
Claims (5)
1. the preparation method of a high-strength carbon fiber, it is characterized in that, take stabilization fiber cyclisation degree as 82 ± 5% and aromatization index be regulation and control foundations as 65 ± 5%, the oxysome volume concentrations of controlling stabilization atmosphere is 21.1%-22.8%, prepares high-strength carbon fiber.
2. according to the method for claim 1, it is characterized in that, the cyclisation degree of stabilization fiber and aromatization index numerical value adopt respectively infrared spectrum and X-ray diffraction analysis to measure, stabilization fiber is rubbed as short fiber, dry 72h for 60 ℃, carry out infrared spectrum analysis, obtain infrared signature peak data; Carry out X-ray diffraction analysis, obtain characteristic diffraction peak data;
Computing formula is: η=0.29*I
1630/ (0.29*I
1630+ I
2240), AI=I
22.5/ (I
22.5+ I
17), I wherein
1630for 1630cm
-1place-C=N stretching vibration characteristic absorption peak intensity, I
2240for 2240cm
-1place-the characteristic absorption peak intensity of C ≡ N stretching vibration; I
17being that fiber (100) crystal face diffraction maximum is located in 2 θ=17 °, is the characteristic diffraction peak of cyano functional group, I
22.5it is the characteristic diffraction peak of the 2 θ=22.5 ° trapezium structure locating to form in fiber.
3. according to the method for claim 1, it is characterized in that, under the stabilization condition of 180～300 ℃, polyacrylonitrile copolymer fibre is carried out to stabilization and follow-up 300～1600 ℃ of conventional carbonization treatment, obtain TENSILE STRENGTH higher than the carbon fiber of 3.75GPa, under described stabilization condition, a certain temperature spot or a certain temperature range internal control oxygen gas volume concentrations are 21.1%-22.8%.
4. according to the method for claim 3, it is characterized in that, polyacrylonitrile copolymer fibre tow adopts the fiber of dry method, wet method or dry wet method spinning, and fibre bundle is 1～320K.
5. according to the method for claim 3, it is characterized in that, polyacrylonitrile copolymer fibre, except containing acrylonitrile monemer, also contains one or more polymer monomers: acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylicacidandesters class, acrylamide, methylene succinic acid, Methacrylamide, acrolein, methylacrolein, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone.
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