CN104790070A - Method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation - Google Patents
Method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation Download PDFInfo
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Abstract
The invention relates to a method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation. The method comprises the following steps: carrying out appropriate doses of gamma ray irradiation for polyacrylonitrile fiber in air, vacuum or inert atmosphere, and thus generating part of cyclization and crosslinking structure; carrying out thermal oxidation stabilization for 0-100 min in air atmosphere to achieve full cyclization and crosslinking; carrying out low-temperature carbonization and high-temperature carbonization so as to prepare the high-performance carbon fiber. The method carries out pre-irradiation treatment before thermal stabilization, so that the thermal stabilization time can be shortened, the production efficiency can be improved, and polyacrylonitrile molecules can form a rigid structure with a regular structure and strong heat resistance. Higher rigid drafting can be applied in the thermal stabilization process, the orientation degree graphite-like sheets in the carbon fiber is facilitated, and the high-performance carbon fiber is prepared.
Description
Technical field
The invention belongs to the preparation field of polyacrylonitrile carbon fiber, particularly a kind of gamma-ray irradiation prepares the method for polyacrylonitrile carbon fiber.
Background technology
Polyacrylonitrile (PAN) base carbon fibre tool the is high excellent properties such as have intensity, high-modulus, density little, high temperature resistant, be widely used in the civil area such as the field such as space flight, science and techniques of defence and physical culture, traffic, building, pressure vessel, wind-power electricity generation, become the main flow of world today's carbon fiber development, account for more than 90% of carbon fiber market.
Carbon fiber precursor, before carbonization, through thermostabilization process, also referred to as pre-oxidation, to obtain having the not molten Heat-resistant stable structure of not firing of trapezium structure, thus will ensure carrying out smoothly of carbonisation, and then obtains high performance carbon fiber.But, although the degree of molecular orientation of PAN precursor can reach more than 90% by means such as high-temperature vapor drawing-offs, but due to its flexible molecules, disorientation can be produced because of strand thermal contraction in thermostabilization process, affect the mechanical property of final carbon fiber.In order to the deorientation suppressing this thermal contraction to cause, current way is carried out in stabilization process at carbon fiber precursor, applies suitable rigidity drawing-off simultaneously.Patent 201110079058.6 proposes first polyacrylonitrile fibril to be carried out pre-cyclisation under an inert atmosphere, then under inert gas and steam atmosphere, the drawing-off of cyclisation plasticity is carried out, in air atmosphere, finally carry out fully oxidized being cross-linked obtain pre-oxidized fibers, thus improve the degree of orientation of pre-oxidized fibers.But polyacrylonitrile molecule is in the heat treatment process of inert gas, the disorientation of strand is avoided to be impossible completely.That is, when heat treatment temperature is higher than the glass transition temperature (T of polyacrylonitrile
g pAN≈ 80 DEG C), the effect generation shrinkage stress that the strand of high orientation will recover due to entropy causes filament contraction.Therefore, if polyacrylonitrile can be made the cyclisation of cyano group to occur below glass transition temperature and be cross-linked, produce semirigid structure, so effectively will suppress the axial shrinkage of PAN molecule in thermostabilization process.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that gamma-ray irradiation prepares polyacrylonitrile carbon fiber, the present invention carried out pre-irradiation process before thermostabilization, can not only shortening heat stabilizing take, enhance productivity, and the rigid structure that the heat resistance of polyacrylonitrile molecule formation compound with regular structure is strong can be made, higher rigidity drawing-off can be applied in thermostabilization process, contribute to improving class graphite synusia degree of orientation in carbon fiber, prepare high-performance carbon fibre.
A kind of gamma-ray irradiation of the present invention prepares the method for polyacrylonitrile carbon fiber, comprising:
(1) polyacrylonitrile fibre precursor is carried out gamma-ray irradiation under air, vacuum or inert atmosphere protection, obtain the fiber of radiation treatment;
(2) under condition of normal pressure, the fiber of above-mentioned radiation treatment is carried out thermostabilization process, obtain polyacrylonitrile thermostabilization fiber;
(3) polyacrylonitrile thermostabilization fiber is carried out low-temperature carbonization in nitrogen atmosphere, temperature is 300-900 DEG C, time is 1-20min, and then high temperature cabonization is carried out in nitrogen atmosphere, temperature is 1300 DEG C, time is 0.5-4min, and whole carbonisation tension force controls, at 5-150MPa, to obtain polyacrylonitrile carbon fiber.
In described step (1) polyacrylonitrile fibre precursor be containing acrylonitrile mass percent higher than 90% polyacrylonitrile fibre precursor.
In described step (1), polyacrylonitrile fibre is the polyacrylonitrile fibre precursor that can be used as carbon fiber precursor.
The one in acrylamide copolymer, methylmethacrylate copolymer is contained in polyacrylonitrile fibre precursor in described step (1).
In described step (1), inert atmosphere is one or more in nitrogen, helium, argon gas, carbon dioxide.
In described step (1), gamma-ray irradiation is specially: radiation source is
60co gamma-rays, dosage of radiation is 10 ~ 1000kGy, and radiation dose rate is 0.01 ~ 10kGy/h.
In described step (2), thermostabilization process is specially: temperature is 150-300 DEG C, and atmosphere is air atmosphere, and tension force controls at 0 ~ 60MPa, and the processing time is 0 ~ 100min.
In described step (2), thermostabilization process is carried out in Continuous Heat reacting furnace.
In described step (3), low-temperature carbonization process tension force controls is 5 ~ 30MPa; It is 10 ~ 150MPa that high temperature cabonization tension force controls.
Polyacrylonitrile fibre is carried out the gamma-ray irradiation of suitable dose by the present invention in air, vacuum or inert atmosphere, generating portion cyclisation, cross-linked structure, then the stabilization of 0 ~ 100min is carried out in air atmosphere, make its sufficient cyclisation and be cross-linked, and then preparing high-performance carbon fibre through low-temperature carbonization and high temperature cabonization process.
beneficial effect
The present invention carried out gamma-ray irradiation process before polyacrylonitrile fibre thermostabilization, and polyacrylonitrile molecule can be made at T
gfollowing generating portion cyclisation is with crosslinked, form semirigid structure, be referred to as " cold crosslinked ", and then be cross-linked containing making it abundant cyclisation in oxygen heat treatment process, stabilizing take can not only be shortened like this, enhance productivity, and higher rigidity drawing-off can be applied in thermostabilization process, contribute to improving class graphite synusia degree of orientation in carbon fiber, prepare high-performance carbon fibre.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Choose the polyacrylonitrile fibril (be designated as: precursor A) of 3K (i.e. 3000 monofilament number/bundles) containing acrylamide copolymer, first carry out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 1kGy/h, exposure time 50h, total irradiation dose is 50kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 200 DEG C, 220 DEG C, 235 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 15min, amounts to 75min.Tension force controls as follows: first and second temperature range tension force controls as 30MPa, and three-temperature-zone tension force controls as 24MPa, and three-temperature-zone tension force controls as 30MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 15min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 2min, and tension force controls at 30MPa.
Respectively radiation modification fiber, thermostabilization fiber and carbon fiber are shredded powdered, adopt means of differential scanning calorimetry (DSC) and X-ray diffractometer (XRD) to analyze cyclisation degree and the degree of orientation of fiber; Adopted by carbon fiber epoxy resin E-51/ acetone/triethylene tetramine (10:7:1) liquid of preparation the solidification of self-control fiber multifilament gluing machine to be prepared into carbon fiber multifilament batten, then according to GB3362-82, Mechanics Performance Testing is carried out to carbon fiber samples.
The fiber sample structural behaviour parameter prepared according to above-mentioned steps lists in table 1.
Embodiment 2
Fiber sample, with embodiment 1, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 1kGy/h, exposure time 100h, total irradiation dose is 100kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 200 DEG C, 220 DEG C, 235 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 12.5min, amounts to 60min.Tension force controls as follows: first and second temperature range tension force controls as 35MPa, and three-temperature-zone tension force controls as 26MPa, and three-temperature-zone tension force controls as 35MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 12.5min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.7min, and tension force controls at 30MPa.Other steps are with embodiment 1.
Embodiment 3
Fiber sample, with embodiment 1, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 2kGy/h, exposure time 100h, total irradiation dose is 200kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 200 DEG C, 220 DEG C, 235 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 11min, amounts to 55min.Tension force controls as follows: first and second temperature range tension force controls as 37.5MPa, and three-temperature-zone tension force controls as 28MPa, and three-temperature-zone tension force controls as 37.5MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 11min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.5min, and tension force controls at 35MPa.Other steps are with embodiment 1.
Embodiment 4
Fiber sample, with embodiment 1, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 5kGy/h, exposure time 60h, total irradiation dose is 300kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 200 DEG C, 220 DEG C, 235 DEG C, 245 DEG C and 265 DEG C five temperature ranges, the time of staying of each warm area is 11min, amounts to 55min.Tension force controls as follows: first and second temperature range tension force controls as 40MPa, and three-temperature-zone tension force controls as 32MPa, and three-temperature-zone tension force controls as 40MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 11min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.5min, and tension force controls at 40MPa.Other steps are with embodiment 1.
Embodiment 5
Fiber sample, with embodiment 1, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 4kGy/h, exposure time 100h, total irradiation dose is 400kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 200 DEG C, 220 DEG C, 235 DEG C, 245 DEG C and 265 DEG C five temperature ranges, the time of staying of each warm area is 11min, amounts to 55min.Tension force controls as follows: first and second temperature range tension force controls as 37.5MPa, and three-temperature-zone tension force controls as 28MPa, and three-temperature-zone tension force controls as 37.5MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 11min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.5min, and tension force controls at 35MPa.Other steps are with embodiment 1.
Embodiment 6
Choose the polyacrylonitrile fibril (be designated as: precursor B) of commercially available business 3K containing methylmethacrylate copolymer, first carry out in vacuum atmosphere
60co gamma-ray irradiation, radiation dose rate 1kGy/h, exposure time 100h, total irradiation dose is 100kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 190 DEG C, 225 DEG C, 240 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 12.5min, amounts to 60min.Tension force controls as follows: first and second temperature range tension force controls as 35MPa, and three-temperature-zone tension force controls as 26MPa, and three-temperature-zone tension force controls as 35MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 12.5min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.7min, and tension force controls at 30MPa.Other steps are with embodiment 1.
The fiber sample structure and performance parameters prepared according to above-mentioned steps lists in table 2.
Embodiment 7
Fiber sample, with embodiment 6, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 4kGy/h, exposure time 50h, total irradiation dose is 200kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 190 DEG C, 225 DEG C, 240 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 11min, amounts to 55min.Tension force controls as follows: first and second temperature range tension force controls as 37.5MPa, and three-temperature-zone tension force controls as 28MPa, and three-temperature-zone tension force controls as 37.5MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 11min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 1.5min, and tension force controls at 35MPa.Other steps are with embodiment 1.
Embodiment 8
Fiber sample, with embodiment 6, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 4kGy/h, exposure time 100h, total irradiation dose is 400kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Then the polyacrylonitrile fibre of radiation modification is carried out in air dielectric to the thermostabilization process of 190 DEG C, 225 DEG C, 240 DEG C, 250 DEG C and 280 DEG C five temperature ranges, the time of staying of each warm area is 6min, amounts to 30min.Tension force controls as follows: first and second temperature range tension force controls as 45MPa, and three-temperature-zone tension force controls as 28.5MPa, and three-temperature-zone tension force controls as 45MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 6min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 0.8min, and tension force controls at 30MPa.Other steps are with embodiment 1.
Embodiment 9
Fiber sample, with embodiment 6, first carries out in air atmosphere
60co gamma-ray irradiation, radiation dose rate 4kGy/h, exposure time 200h, total irradiation dose is 800kGy, obtains " cold crosslinked " polyacrylonitrile fibre of radiation modification.Radiation modification polyacrylonitrile fibre is directly entered low-temperature carbonization under nitrogen protection, and instant heating stabilizing take is 0min, and low-temperature carbonization temperature is 300 DEG C, 423 DEG C, 550 DEG C and 850 DEG C, and the time of staying is 10min, and tension force controls as 12MPa; Then enter the high temperature carbonization furnace as 1300 DEG C, the time of staying is 1.3min, and other steps are with embodiment 1.
Comparative example 1
Polyacrylonitrile fibre, with embodiment 1, is directly entered the thermostabilization process of air atmosphere by fiber sample, and temperature range is 200 DEG C, 220 DEG C, 235 DEG C, 250 DEG C and 280 DEG C, and the time of staying of each warm area is 17.5min, amounts to 87.5min.Tension force controls: first and second temperature range tension force controls as 27MPa, and three-temperature-zone tension force controls as 22MPa, and three-temperature-zone tension force controls as 27MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 17.5min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 2.3min, and tension force controls at 30MPa.Other steps are with embodiment 1.
Comparative example 2
Polyacrylonitrile fibre, with embodiment 6, is directly entered the thermostabilization process of air atmosphere by fiber sample, and temperature range is 200 DEG C, 220 DEG C, 235 DEG C, 250 DEG C and 280 DEG C, and the time of staying of each warm area is 17.5min, amounts to 87.5min.Tension force controls: first and second temperature range tension force controls as 27MPa, and three-temperature-zone tension force controls as 22MPa, and three-temperature-zone tension force controls as 27MPa.Obtain thermostabilization fiber.By thermostabilization fiber under nitrogen protection, carry out low-temperature carbonization at 400 DEG C, 450 DEG C, 600 DEG C and 850 DEG C of temperature, the time of staying is 17.5min, and tension force controls as 12MPa; Finally enter the high temperature carbonization furnace of 1300 DEG C, the time of staying is 2.3min, and tension force controls at 30MPa.Other steps are with embodiment 1.
The present invention carried out polyacrylonitrile fibre heat before thermostabilization
60the modification of Co gamma-ray irradiation, make it generating portion cyclisation before the heat treatment, cross-linked structure, then in air dielectric, sufficient stabilization is carried out, stabilizing take can not only be shortened like this, enhance productivity, and higher rigidity drawing-off can be applied in thermostabilization process, contribute to improving class graphite synusia degree of orientation in carbon fiber, prepare high-performance carbon fibre.
Table 1
Table 2
Claims (8)
1. prepare a method for polyacrylonitrile carbon fiber with gamma-ray irradiation, comprising:
(1) polyacrylonitrile fibre precursor is carried out gamma-ray irradiation under air, vacuum or inert atmosphere protection, obtain the fiber of radiation treatment;
(2) under condition of normal pressure, the fiber of above-mentioned radiation treatment is carried out thermostabilization process, obtain polyacrylonitrile thermostabilization fiber;
(3) polyacrylonitrile thermostabilization fiber is carried out low-temperature carbonization in nitrogen atmosphere, temperature is 300-900 DEG C, time is 1-20min, and then high temperature cabonization is carried out in nitrogen atmosphere, temperature is 1300 DEG C, time is 0.5-4min, and whole carbonisation tension force controls, at 5-150MPa, to obtain polyacrylonitrile carbon fiber.
2. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (1) polyacrylonitrile fibre precursor be containing acrylonitrile mass percent higher than 90% polyacrylonitrile fibre precursor.
3. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: contain the one in acrylamide copolymer, methylmethacrylate copolymer in described step (1) in polyacrylonitrile fibre precursor.
4. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (1), inert atmosphere is one or more in nitrogen, helium, argon gas, carbon dioxide.
5. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (1), gamma-ray irradiation is specially: radiation source is
60co gamma-rays, dosage of radiation is 10 ~ 1000kGy, and radiation dose rate is 0.01 ~ 10kGy/h.
6. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (2), thermostabilization process is specially: temperature is 150-300 DEG C, atmosphere is air atmosphere, tension force controls at 0 ~ 60MPa, and the processing time is 0 ~ 100min.
7. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (2), thermostabilization process is carried out in Continuous Heat reacting furnace.
8. a kind of gamma-ray irradiation according to claim 1 prepares the method for polyacrylonitrile carbon fiber, it is characterized in that: in described step (3), low-temperature carbonization process tension force controls is 5 ~ 30MPa; It is 10 ~ 150MPa that high temperature cabonization tension force controls.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192362A (en) * | 2016-07-19 | 2016-12-07 | 仇颖超 | A kind of preparation method of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber |
| CN108396548A (en) * | 2017-02-04 | 2018-08-14 | 中国科学院上海应用物理研究所 | A kind of big tow PAN-based stabilized fiber, large-tow carbon fiber and preparation method thereof |
| CN108396549A (en) * | 2017-02-04 | 2018-08-14 | 中国科学院上海应用物理研究所 | A kind of big tow PAN-based stabilized fiber, large-tow carbon fiber and preparation method thereof |
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| CN109306552A (en) * | 2017-07-28 | 2019-02-05 | 北京化工大学 | High-strength high-modules carbon fibre and preparation method thereof |
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| CN109750487A (en) * | 2019-02-01 | 2019-05-14 | 中国工程物理研究院核物理与化学研究所 | A kind of carbon fiber multifilament radiates preprocess method containing nitrogen atmosphere |
| CN110306335A (en) * | 2019-05-10 | 2019-10-08 | 海盐县硕创服装研究所 | Moisture-absorption polyacrylonitrile fiber |
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| DE102019105292A1 (en) * | 2019-03-01 | 2020-09-03 | Dralon Gmbh | Process for the ionizing irradiation of textile polyacrylonitrile fibers and their use as a carbon fiber precursor |
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| CN113215684A (en) * | 2021-05-20 | 2021-08-06 | 北京化工大学 | Method for preparing polyacrylonitrile-based thermo-oxidative stabilized fiber |
| CN113930927A (en) * | 2021-09-22 | 2022-01-14 | 浙江得威德环保科技股份有限公司 | Method for preparing carbonized felt from PAN (polyacrylonitrile) -based pre-oxidized fiber needled felt by combined power method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260575A (en) * | 2008-04-17 | 2008-09-10 | 东华大学 | Pre-oxidation method for carbon fiber precursor polyacrylnitrile fiber |
| CN101798392A (en) * | 2009-12-11 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using gamma ray irradiation |
| CN101798747A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using electron beam irradiation |
| CN104233514A (en) * | 2014-09-29 | 2014-12-24 | 刘剑洪 | Polyacrylonitrile carbon fiber and preparation method thereof |
-
2015
- 2015-04-17 CN CN201510186213.2A patent/CN104790070A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260575A (en) * | 2008-04-17 | 2008-09-10 | 东华大学 | Pre-oxidation method for carbon fiber precursor polyacrylnitrile fiber |
| CN101798392A (en) * | 2009-12-11 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using gamma ray irradiation |
| CN101798747A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using electron beam irradiation |
| CN104233514A (en) * | 2014-09-29 | 2014-12-24 | 刘剑洪 | Polyacrylonitrile carbon fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 季加强等: "γ射线辐照对聚丙烯腈原丝及其预氧化反应的影响", 《合成纤维工业》 * |
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| CN108396548A (en) * | 2017-02-04 | 2018-08-14 | 中国科学院上海应用物理研究所 | A kind of big tow PAN-based stabilized fiber, large-tow carbon fiber and preparation method thereof |
| CN108396549A (en) * | 2017-02-04 | 2018-08-14 | 中国科学院上海应用物理研究所 | A kind of big tow PAN-based stabilized fiber, large-tow carbon fiber and preparation method thereof |
| CN109306553A (en) * | 2017-07-28 | 2019-02-05 | 北京化工大学 | The method for preparing polyacrylonitrile carbon fiber |
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| CN108754673A (en) * | 2018-05-08 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | A kind of high stretch modulus graphite fibre and preparation method thereof |
| CN111088560A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based large-tow carbon fiber |
| CN111286816A (en) * | 2018-12-10 | 2020-06-16 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon fiber with smooth surface |
| CN111286816B (en) * | 2018-12-10 | 2022-11-29 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon fiber with smooth surface |
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| DE102019105292A1 (en) * | 2019-03-01 | 2020-09-03 | Dralon Gmbh | Process for the ionizing irradiation of textile polyacrylonitrile fibers and their use as a carbon fiber precursor |
| CN110306335A (en) * | 2019-05-10 | 2019-10-08 | 海盐县硕创服装研究所 | Moisture-absorption polyacrylonitrile fiber |
| CN110484988A (en) * | 2019-07-31 | 2019-11-22 | 北京化工大学常州先进材料研究院 | A kind of method of modified acrylic fibre |
| CN112709093A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of carbon fiber paper |
| CN113215684A (en) * | 2021-05-20 | 2021-08-06 | 北京化工大学 | Method for preparing polyacrylonitrile-based thermo-oxidative stabilized fiber |
| CN113930927A (en) * | 2021-09-22 | 2022-01-14 | 浙江得威德环保科技股份有限公司 | Method for preparing carbonized felt from PAN (polyacrylonitrile) -based pre-oxidized fiber needled felt by combined power method |
| CN113930927B (en) * | 2021-09-22 | 2023-06-13 | 浙江得威德环保科技股份有限公司 | Method for preparing carbonized felt by PAN-based pre-oxidized fiber needled felt by combined power method |
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