CN104818546A - Preparation method of high-strength high-modulus graphite fiber - Google Patents
Preparation method of high-strength high-modulus graphite fiber Download PDFInfo
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Abstract
The invention relates to the field of organic high polymers, particularly a preparation method of a high-strength high-modulus graphite fiber, which is characterized by comprising the following steps: applying 2-3 times of drawing on a polyacrylonitrile copolymer fiber in the steam drawing stage to obtain grey yarn with the degree of orientation of 91-93%; preoxidizing the obtained grey yarn at 180-280 DEG C in an air atmosphere, and carrying out heat treatment in a six-stage gradient heating mode for 60-110 minutes to obtain a preoxidized fiber with the density of 1.34+/-0.02 g/cm<3>; carrying out low-temperature carbonization on the preoxidized fiber at 300-900 DEG C in a nitrogen protective atmosphere at the drawing ratio of 0-4% for 3+/-1.5 minutes, and carrying out high-temperature carbonization on the obtained fiber at 1000-1800 DEG C at the drawing ratio of -4-0% for 3+/-1.5 minutes to obtain the carbon fiber with the carbon content of greater than 96% and the diameter of 7 mu m; and graphitizing the obtained carbon fiber at 2200-2500 DEG C in an inert gas protective atmosphere at the drawing ratio of 1-5% for 2+/-1 minutes, thereby obtaining the graphite fiber.
Description
Technical field
The present invention relates to Carbon Fiber Technology field, specifically a kind of preparation method of high strength and modulus graphite fibre.
Background technology
We know, the preparation process of polyacrylonitrile-radical (PAN) graphite fibre mainly comprises the stages such as precursor shaping, pre-oxidation, low-temperature carbonization, high temperature cabonization and graphitization.The size of graphite microcrystal, distribution, defect level and orientation etc. determine its performance, and the structure of graphite fibre depends on the structure improvement degree of carbon fiber, therefore, the carbon fiber of obtained structure improvement can be carried out by the structure controlling precursor and pre-oxidized fibers, thus obtain the graphite fibre of structure improvement and excellent performance.
The thin dawnization of precursor has become and has improved one of precursor intensity and the Major Technology producing high-performance carbon fibre, in order to prepare high-intensity fine denier precursor, steam drafting need be carried out to PAN fibre bundle under some tension, namely under the condition ensureing fibre strength, requirement according to the fiber finer dawn suitably adjusts drafting multiple, and general steam drafting multiple is between 2 ~ 3.Drafting multiple, lower than 2, can not ensure that the intensity of fiber reaches requirement, then easily produces the excessive phenomenon of drawing-off higher than 3 times.Steam drafting makes the morphosis of fiber there occurs change, under the effect of drafting stress and fuel factor, the mobility of macromolecular chain segment increases, various construction unit is along fiber axis to assembling, resetting, molecular chain orientation degree uprises, strand is stretched, and makes more strand in fiber be in optimum stress state.Therefore, along with the increase of drafting multiple, precursor degree of orientation raises, and the intensity of fiber improves.
In preoxidation process, controlling oxidization fiber density is conventional effective method.In oxidization fiber, Control for Oxygen Content is 8 ~ 10%, and its density should control at 1.32 ~ 1.36g/cm
3between.When oxidization fiber density is lower than 1.32g/cm
3time, pre-oxidation is insufficient, and pre-oxidized fibers easily occurs to melt also at carbonation stage, introduces defect, cause carbon fiber performance to reduce in PAN macromolecular chain.When oxidization fiber density is higher than 1.36g/cm
3time, pre-oxidation is excessive, and the oxygen element that PAN strand combines is excessive, and in carbonisation, oxygen is with H
2o, CO, CO
2small molecular form runaway, PAN strand introduces defect, cause carbon fiber density decline and performance reduction.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high strength and modulus graphite fibre is provided, control the drafting multiple of fiber in the steam drafting stage, obtain the precursor that the degree of orientation is higher, control precursor at the technological parameter in pre-oxidation stage, obtain the pre-oxidized fibers of structure improvement, control temperature and the tension force in high temperature cabonization stage, obtain the carbon fiber of phosphorus content more than 96%, thus obtained high strength and modulus graphite fibre.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of preparation method of high strength and modulus graphite fibre, it is characterized in that, comprise the following steps: polyacrylonitrile copolymer fibre to apply the drawing-off of 2 ~ 3 times in the steam drafting stage, obtain the degree of orientation 91 ~ 93% precursor.By the precursor pre-oxidation in 180 ~ 280 DEG C of temperature ranges in air atmosphere obtained, adopt 6 sections of gradient increased temperature mode heat treatment 60 ~ 110min, obtained density is 1.34 ± 0.02g/cm
3pre-oxidized fibers.By gained pre-oxidized fibers under nitrogen protection, under the draw ratio of 0 ~ 4%, low-temperature carbonization 3 ± 1.5min at 300 ~ 900 DEG C; by gained fiber high temperature cabonization 3 ± 1.5min at 1000 ~ 1800 DEG C; draw ratio is-4 ~ 0%, obtains phosphorus content and is greater than 96%, and diameter is the carbon fiber of 7 μm.By gained carbon fiber under inert gas shielding, graphitization 2 ± 1min at 2200 ~ 2500 DEG C, draw ratio is 1 ~ 5%, obtains graphite fibre.
Above-mentioned polyacrylonitrile copolymer fibre bundle can be divided into 1 ~ 48K.Above-mentioned polyacrylonitrile copolymer fibre is except containing except acrylonitrile monemer, also comprises the copolymer of one or more following monomers: itaconic acid, acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and ester class thereof, acrylamide, methylene succinic acid, Methacrylamide, acrolein, methylacrolein, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone.
The invention has the beneficial effects as follows, carry out mechanical property sign to prepared graphite fibre tow, result shows: the degree of orientation is the precursor of 91 ~ 93%, and obtaining density through pre-oxidation is 1.34 ± 0.02g/cm
3pre-oxidized fibers, then obtain phosphorus content through high temperature cabonization and be greater than 96%, diameter is the carbon fiber of 7 μm, and at 2200 ~ 2500 DEG C, carry out graphitization obtain TENSILE STRENGTH higher than 4.5GPa, stretch modulus is higher than the graphite fibre of 390 GPa.Pass through examples prove, the size of the degree of orientation of precursor, pre-oxidized fibers density and carbon fiber phosphorus content will affect the stuctures and properties of graphite fibre, the structure of graphite fibre can being improved by the phosphorus content controlling the degree of orientation of precursor, the density of pre-oxidized fibers and carbon fiber and improve its mechanical property, having good directive significance to preparing high strength and modulus graphite fibre.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
The Tuozhan Fiber Co., Ltd., Weihai selecting wet method to spin produces, containing the PAN copolymer fibre of more than 90% acrylonitrile monemer component, (its tow is 12K, copolymer composition (wt%) is: acrylonitrile (AN): methyl acrylate (MA): itaconic acid (IA)=96:2:2), the drawing-off of 2.1 times is applied in the steam drafting stage, the obtained degree of orientation is the precursor of 91.5%, by precursor in air dielectric, adopt 190 DEG C, 210 DEG C, 225 DEG C, 235 DEG C, 245 DEG C, 265 DEG C of six sections of pre-oxidation treatment, the time of staying is 90min, draw ratio is 1%, obtaining density is 1.34g/cm
3pre-oxidized fibers, by pre-oxidized fibers under the protection of nitrogen, carry out low-temperature carbonization at 300 ~ 900 DEG C of temperature, the time of staying is 3min, apply+2% draw ratio, apply the draw ratio of-3% at 1000 ~ 1800 DEG C of temperature, high temperature cabonization 3min, obtained phosphorus content is 97.0%, and diameter is the carbon fiber of 7 μm, at 2400 DEG C of temperature, carry out graphitization, and the time of staying is 2.5min, applies+2% draw ratio, obtains graphite fibre.Graphite fibre epoxy resin E44/ acetone/triethylene tetramine (10:15:1) the liquid gluing of preparation is cured as strip, then according to GB GB/T 3362-2005, Mechanics Performance Testing is carried out to corresponding carbon fiber samples, the results are shown in Table 1.
Embodiment 2:
Adopt the 12K PAN copolymer fibre that Tuozhan Fiber Co., Ltd., Weihai produces, apply the drawing-off of 2.3 times in the steam drafting stage, the obtained degree of orientation is the precursor of 92.2%, and other technological parameter and operation, with embodiment 1, obtain graphite fibre, the results are shown in Table 1.
Embodiment 3:
Adopt the 12K PAN copolymer fibre that Tuozhan Fiber Co., Ltd., Weihai produces, apply the drawing-off of 2.5 times in the steam drafting stage, the obtained degree of orientation is the precursor of 92.8%, and other technological parameter and operation, with embodiment 1, obtain graphite fibre, the results are shown in Table 1.
Embodiment 4:
Adopt the 12K PAN copolymer fibre that Tuozhan Fiber Co., Ltd., Weihai produces, by precursor in air dielectric, adopt 190 DEG C, 205 DEG C, 220 DEG C, 233 DEG C, 245 DEG C, 260 DEG C six sections of pre-oxidation treatment, the time of staying is 100min, draw ratio is 1.5%, and obtaining density is 1.33g/cm
3pre-oxidized fibers, other technological parameter and operation with embodiment 2, obtain graphite fibre, the results are shown in Table 1.
Embodiment 5:
Adopt the 12K PAN copolymer fibre that Tuozhan Fiber Co., Ltd., Weihai produces, by precursor in air dielectric, adopt 190 DEG C, 210 DEG C, 230 DEG C, 245 DEG C, 255 DEG C, 270 DEG C six sections of pre-oxidation treatment, the time of staying is 85min, draw ratio is 0.5%, and obtaining density is 1.35g/cm
3pre-oxidized fibers, other technological parameter and operation with embodiment 2, obtain graphite fibre, the results are shown in Table 1.
Embodiment 6:
The 3K PAN copolymer fibre (copolymer composition is identical with 12K) adopting Tuozhan Fiber Co., Ltd., Weihai to produce, other technological parameter and operation, with embodiment 1, obtain graphite fibre, the results are shown in Table 1.
Embodiment 7:
The 3K PAN copolymer fibre (copolymer composition is identical with 12K) adopting Tuozhan Fiber Co., Ltd., Weihai to produce, other technological parameter and operation, with embodiment 2, obtain graphite fibre, the results are shown in Table 1.
Embodiment 8:
The 3K PAN copolymer fibre (copolymer composition is identical with 12K) adopting Tuozhan Fiber Co., Ltd., Weihai to produce, other technological parameter and operation, with embodiment 3, obtain graphite fibre, the results are shown in Table 1.
The mechanical performance data of table 1 graphite fibre
Can draw to draw a conclusion according in the corresponding graphite fibre mechanical performance data of table 1 embodiment:
As can be seen from TENSILE STRENGTH and the stretch modulus of the corresponding graphite fibre of embodiment 1 ~ 3 and 6 ~ 8, when oxidization fiber density is 1.34g/cm
3time, with the increase of the precursor degree of orientation, TENSILE STRENGTH and the stretch modulus of gained graphite fibre increase gradually.
As can be seen from TENSILE STRENGTH and the stretch modulus of the corresponding graphite fibre of embodiment 2,4 and 5, when the precursor degree of orientation is 92.2%, with the increase of oxidization fiber density, the TENSILE STRENGTH of gained graphite fibre and stretch modulus first increases and then decreases; When oxidization fiber density is 1.34g/cm
3time, TENSILE STRENGTH and the stretch modulus of gained graphite fibre are the highest.
As can be seen from TENSILE STRENGTH and the stretch modulus of the corresponding graphite fibre of embodiment 1 ~ 8, when the precursor degree of orientation is 91 ~ 93%, oxidization fiber density is 1.34 ± 0.02g/cm
3time, the performance of gained graphite fibre is higher, and TENSILE STRENGTH reaches 4.5 more than Gpa, and stretch modulus reaches more than 390GPa.
Claims (3)
1. a preparation method for high strength and modulus graphite fibre, is characterized in that, comprises the following steps: polyacrylonitrile copolymer fibre to apply the drawing-off of 2 ~ 3 times in the steam drafting stage, obtain the degree of orientation 91 ~ 93% precursor; By the precursor pre-oxidation in 180 ~ 280 DEG C of temperature ranges in air atmosphere obtained, adopt 6 sections of gradient increased temperature mode heat treatment 60 ~ 110min, obtained density is 1.34 ± 0.02g/cm
3pre-oxidized fibers; By gained pre-oxidized fibers under nitrogen protection, under the draw ratio of 0 ~ 4%, low-temperature carbonization 3 ± 1.5min at 300 ~ 900 DEG C, by gained fiber high temperature cabonization 3 ± 1.5min at 1000 ~ 1800 DEG C, draw ratio is-4 ~ 0%, obtains phosphorus content and is greater than 96%, and diameter is the carbon fiber of 7 μm; By gained carbon fiber under inert gas shielding, graphitization 2 ± 1min at 2200 ~ 2500 DEG C, draw ratio is 1 ~ 5%, obtains graphite fibre.
2. the preparation method of high strength and modulus graphite fibre according to claim 1, is characterized in that described polyacrylonitrile copolymer fibre bundle can be divided into 1 ~ 48K.
3. the preparation method of high strength and modulus graphite fibre according to claim 1, it is characterized in that described polyacrylonitrile copolymer fibre is for except containing acrylonitrile monemer, also comprise the copolymer of one or more following monomers: itaconic acid, acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and ester class thereof, acrylamide, methylene succinic acid, Methacrylamide, acrolein, methylacrolein, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105401262A (en) * | 2015-12-21 | 2016-03-16 | 中复神鹰碳纤维有限责任公司 | Middle-modulus carbon fiber preparation method based on rapid spinning and high denier precursor |
| CN108193324A (en) * | 2017-12-26 | 2018-06-22 | 宜兴市天宇世纪高新科技有限公司 | A kind of production technology of polyacrylonitrile-based carbon fibre |
| CN109252250A (en) * | 2018-08-06 | 2019-01-22 | 威海拓展纤维有限公司 | The carbonization treatment method of polyacrylonitrile-based carbon fibre |
| CN109280998A (en) * | 2018-09-28 | 2019-01-29 | 威海拓展纤维有限公司 | A kind of preparation method of PAN base high-strength and high-modulus type carbon fiber |
| CN109280997A (en) * | 2018-09-20 | 2019-01-29 | 北京化工大学 | The high-strength high-modules carbon fibre and preparation method thereof of low degree of graphitization |
| CN109402790A (en) * | 2018-09-20 | 2019-03-01 | 北京化工大学 | High-orientation polyacrylonitrile fibril and its preparation method and application for obtaining high-strength high-modules carbon fibre |
| CN109468712A (en) * | 2018-10-24 | 2019-03-15 | 北京化工大学 | The method that high modulus carbon fiber and regulation thermostabilization fiber oxygen ring structure prepare high modulus carbon fiber |
| CN109989127A (en) * | 2017-12-31 | 2019-07-09 | 福建恒安集团有限公司 | A kind of hot-wind nonwoven cloth material |
| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105401262A (en) * | 2015-12-21 | 2016-03-16 | 中复神鹰碳纤维有限责任公司 | Middle-modulus carbon fiber preparation method based on rapid spinning and high denier precursor |
| CN108193324A (en) * | 2017-12-26 | 2018-06-22 | 宜兴市天宇世纪高新科技有限公司 | A kind of production technology of polyacrylonitrile-based carbon fibre |
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| CN109280997A (en) * | 2018-09-20 | 2019-01-29 | 北京化工大学 | The high-strength high-modules carbon fibre and preparation method thereof of low degree of graphitization |
| CN109402790A (en) * | 2018-09-20 | 2019-03-01 | 北京化工大学 | High-orientation polyacrylonitrile fibril and its preparation method and application for obtaining high-strength high-modules carbon fibre |
| CN109280998A (en) * | 2018-09-28 | 2019-01-29 | 威海拓展纤维有限公司 | A kind of preparation method of PAN base high-strength and high-modulus type carbon fiber |
| CN109468712A (en) * | 2018-10-24 | 2019-03-15 | 北京化工大学 | The method that high modulus carbon fiber and regulation thermostabilization fiber oxygen ring structure prepare high modulus carbon fiber |
| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
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