CN109402795B - Pre-oxidation method and equipment for improving mechanical property of carbon fiber - Google Patents
Pre-oxidation method and equipment for improving mechanical property of carbon fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/32—Apparatus therefor
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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Abstract
The invention relates to a pre-oxidation process and equipment for improving the mechanical property of carbon fibers, and mainly solves the technical problems that the pre-oxidized fibers are poor in compactness and serious in skin-core structure in the existing carbon fiber preparation process, so that the final carbon fibers are poor in mechanical property and large in dispersion coefficient. Through adopting the pre-oxidation equipment that improves carbon fiber mechanical properties, including the following unit: the device comprises a plurality of pre-oxidation furnaces and a driving unit, wherein each pre-oxidation furnace comprises a furnace tube, a heating wire, a heat insulation layer and a shell; the method is characterized in that the heating wires in the pre-oxidation furnace are non-uniformly wound on the furnace tube, and the winding density is increased along the wire moving direction, so that the temperature difference from the inlet to the outlet of the oxidation furnace can be 10-50 ℃; the technical scheme that the heat-insulating layer with the thickness of 20-200cm is arranged outside the heating gold wire winding layer on the surface of the furnace tube, and the shell is arranged outside the heat-insulating layer better solves the problems and can be used in the industrial production of the polyacrylonitrile-based carbon fiber.
Description
Technical Field
The invention relates to a carbon fiber pre-oxidation process and equipment, which can effectively improve the mechanical property of carbon fiber.
Technical Field
The carbon fiber is a fibrous polymer having a carbon content of 90% or more, which is obtained by converting an organic fiber through a solid-phase reaction. The fiber has a series of excellent performances of high specific strength, high specific modulus, high temperature resistance, chemical corrosion resistance, fatigue resistance, thermal shock resistance, radiation resistance, small specific gravity and the like, and belongs to typical high-performance fibers. The commercial production of high-strength carbon fibers has been realized abroad, but China is still in the stages of development and trial production, and developed countries such as the United states and the Japanese adopt technical blockade to the China, so that the development of related fields of national defense in China is severely restricted. Therefore, the research work of the high-strength carbon fiber is increasingly emphasized.
The preparation process of the carbon fiber comprises polymerization, spinning, pre-oxidation and carbonization, wherein the pre-oxidation process is a key step in the preparation process of the carbon fiber, and the quality of the pre-oxidized fiber directly determines the mechanical property of the final carbon fiber. The non-uniformity of the chemical structure in the pre-oxidation process will lead to defective structures in the carbon fibers, which ultimately affect the mechanical properties. Therefore, in recent years, scientists have studied the influence of the pre-oxidation process on the performance of carbon fiber. The preparation of the homogeneous pre-oxidized fiber is one of the main technical approaches for improving the performance of the carbon fiber at present, four or six pre-oxidation furnaces are generally adopted by domestic scientific research institutions and production enterprises, and the process adjustment flexibility in the pre-oxidation process is insufficient due to the fixed length of the pre-oxidation furnaces. In the pre-oxidation process, the most important influencing factors are time, temperature and drafting, and the three are mutually connected and influenced, so that a lot of troubles are brought to scientific research. For the reasons, the current domestic main research direction is to overcome basic scientific problems and improve equipment at the same time. In the research process of basic scientific problems, the equipment and the process are optimized so as to improve the mechanical property of the carbon fiber.
A method for manufacturing ternary ammonification modified T400 grade 12K carbon fibers (patent number CN201310132151.8) published by Kudzuotao et al introduces a method for manufacturing ternary ammonification modified T400 grade 12K carbon fibers, acrylonitrile, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid are used as comonomers to carry out ternary free radical solution polymerization, and obtained spinning solution is subjected to ammonification modification and then is spun through a 12K spinneret. The filament bundle is subjected to solidification, washing, hot water drafting, oiling and drying, steam drafting and heat setting to prepare the 12K precursor. And carrying out preoxidation and carbonization treatment on the obtained protofilament to obtain the carbon fiber. The invention adopts nontoxic solid powder raw materials as comonomers and performs ammoniation modification treatment on the spinning solution, so that the hydrophilicity and drawability of the spinning solution prepared by the method are obviously improved, and the compactness, the orientation degree and the crystallinity of the protofilament obtained by the spinning process are obviously improved. After the protofilament is subjected to preoxidation treatment, the protofilament is subjected to gradient carbonization in a low-temperature carbonization furnace at 400-750 ℃ and is subjected to drafting treatment, and the prepared carbon fiber has high mechanical property and high hooking strength; a method for preparing high-performance carbon fibers (patent number CN201310021822.3) published by Liujie et al introduces a method for preparing high-strength high-modulus carbon fibers, and belongs to the technical field of carbon fibers. Placing polyacrylonitrile copolymer fiber in a heat treatment furnace for thermal oxidation stabilization, setting the temperature to be 180-280 ℃, setting the total draft rate to be 5-12%, controlling the fiber residence time to be 17-22 minutes in a temperature region of 265-280 ℃ to obtain oxidized fiber, performing low-temperature and high-temperature carbonization treatment to prepare carbon fiber, taking the oxidation reaction index IO in the oxidized fiber as a control index of a chemical structure, and selecting the fiber with the IO value within the range of 33-50% for low-temperature carbonization and high-temperature carbonization treatment to prepare the carbon fiber. The tensile strength of the prepared carbon fiber is higher than 3.5GPa, and the Young modulus is higher than 250 GPa.
The existing technical scheme can effectively improve the mechanical property of the carbon fiber, but the improvement degree is limited, and only the carbon fiber with the performance close to that of the Nippon Dongli company with the brand number of T300 can be prepared. The invention can improve the mechanical property of carbon fiber greatly by modifying the oxidation furnace properly.
Disclosure of Invention
The invention aims to solve the technical problems that the prior carbon fiber pre-oxidation process has more structural defects and lower tensile strength caused by gradient temperature rise, and provides pre-oxidation equipment for improving the mechanical property of carbon fibers. The equipment is used in the preparation process of the polyacrylonitrile-based carbon fiber, and has the advantages of weakening the structural defect of the pre-oxidized fiber, improving the tensile strength and the film stretching amount and reducing the dispersion coefficient.
The invention aims to solve the technical problems that the prior carbon fiber pre-oxidation process has more structural defects and lower tensile strength of carbon fibers caused by gradient temperature rise, and provides a method for improving the mechanical property of the carbon fibers by adopting the pre-oxidation equipment for solving one of the technical problems. The method is used in the preparation process of the polyacrylonitrile-based carbon fiber, and has the advantages of improving the structural uniformity of the pre-oxidized fiber, weakening the structural defects of the pre-oxidized fiber, improving the tensile strength and the amount of a stretched film, reducing the dispersion coefficient and further improving the performance of the final carbon fiber.
In order to solve one of the above technical problems, the invention adopts the technical scheme that: a pre-oxidation device for improving mechanical properties of carbon fibers comprises the following units: the device comprises a plurality of pre-oxidation furnaces and a driving unit, wherein each pre-oxidation furnace comprises a furnace tube, a heating wire, a heat insulation layer and a shell; the method is characterized in that the heating wires in the pre-oxidation furnace are non-uniformly wound on the furnace tube, and the winding density is increased along the wire moving direction, so that the temperature difference from the inlet to the outlet of the oxidation furnace can be 10-50 ℃; the outside of the heating wire winding layer on the surface of the furnace tube is provided with a heat preservation layer with the thickness of 20-200cm, and the outside of the heat preservation layer is provided with a shell.
In the above technical scheme, the furnace tube is preferably a stainless steel furnace tube, the heating wire is preferably a nichrome wire, the heat preservation layer is preferably a rock wool heat preservation layer, and the shell is preferably a stainless steel shell.
In the technical scheme, the nickel-chromium alloy wire is preferably heated electrically; the number of the oxidation furnaces is preferably at least 3, the effective heating length of the pre-oxidation furnace is preferably 2-6m, a driving unit is preferably arranged in the pre-oxidation furnace, and the pre-oxidation fibers are conveyed in the pre-oxidation furnace through the driving unit.
In order to solve the second technical problem, the invention adopts the technical scheme that: a pre-oxidation method for improving mechanical properties of carbon fibers adopts pre-oxidation equipment in any one of the technical schemes for solving the technical problems, and sequentially comprises the following steps: the carbon fiber is obtained by pre-treating, pre-oxidizing in a pre-oxidizing furnace, carbonizing at low temperature, carbonizing at high temperature, treating the surface, sizing, drying and winding after the protofilament is reeled, and the carbon fiber is characterized in that the pre-oxidizing temperature in the pre-oxidizing furnace is 180-plus-260 ℃, and the temperature is gradually and continuously increased along the reeling direction.
In the technical scheme, the effective heating time of the pre-oxidized fiber in the pre-oxidation furnace is preferably 45-120 min; the pre-oxidation furnace is preferably at least 3, the temperature of the first pre-oxidation furnace is 180-220 ℃, and positive drafting is applied to the fibers in the furnace through a driving unit, wherein the drafting ratio is 0 to +8 percent; the temperature of the middle pre-oxidation furnace is 200-250 ℃, and zero drafting is applied through a driving unit; the temperature of the last pre-oxidation furnace is 240-280 ℃, negative drafting is applied through a driving unit, and the drafting ratio is-8% -0; it is further preferred that the initial temperature of the subsequent pre-oxidation furnace is equal to the final temperature of the previous pre-oxidation furnace.
In the above technical solution, the driving unit is preferably installed inside the pre-oxidation oven.
In the technical scheme, after the protofilament is pre-oxidized, the protofilament is preferably carbonized at low temperature of 300-800 ℃ in an inert atmosphere and carbonized at high temperature of 800-1500 ℃ in an inert atmosphere in sequence.
The equipment used in the method is a continuous pre-oxidation furnace, a low-temperature carbonization furnace and a high-temperature carbonization furnace, wherein the number of the continuous pre-oxidation furnaces is 3-8, and polyacrylonitrile fibers continuously run in a stainless steel furnace tube.
The invention has the advantages that: under the condition of not changing the polymerization spinning and carbonization processes, the uniform and continuous temperature rise in the fiber pre-oxidation process is realized only by changing the resistance wire winding mode and the pre-oxidation process of each pre-oxidation furnace, so that the pre-oxidized fiber with the uniform structure can be prepared, and the foundation is laid for preparing the high-performance carbon fiber.
By adopting the technical scheme of the invention, after the polyacrylonitrile precursor is uncoiled, the polyacrylonitrile precursor is preoxidized in the preoxidation furnace under the air atmosphere, the temperature in each preoxidation furnace is continuously changed and gradually increased along the fiber running direction, then low-temperature carbonization is sequentially carried out at 800 ℃ in the presence of inert gas, high-temperature carbonization is carried out at 1500 ℃ in the presence of 900-fold inert gas, and finally carbon fiber is obtained by coiling, wherein the tensile strength of the carbon fiber can reach 5423MPa, and the dispersion coefficient of the tensile strength can reach 2.67%; the tensile modulus can reach 281GPa, and the dispersion coefficient of the tensile modulus can reach 0.68 percent, thereby obtaining better technical effect.
Drawings
FIG. 1 is a schematic view of an oxidation furnace,
wherein 1 is an oxidation furnace tube, the stainless steel material, 2 is a nickel-chromium alloy resistance wire, and 3 is a carbon fiber tow.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
After the polyacrylonitrile precursor is uncoiled, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 180-; the tensile modulus was 261GPa, and the coefficient of variation of the tensile modulus was 1.65%.
[ example 2 ]
After the polyacrylonitrile precursor is uncoiled, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 175-; the tensile modulus was 238GPa, and the coefficient of variation of the tensile modulus was 1.75%.
[ example 3 ]
After the polyacrylonitrile precursor is uncoiled, pre-oxidation is carried out in the air atmosphere, four pre-oxidation furnaces are provided, the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 190 ℃ for 170-; the tensile modulus was 232GPa, and the coefficient of variation of the tensile modulus was 2.68%.
[ example 4 ]
After the polyacrylonitrile precursor is uncoiled, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 175-; the tensile modulus was 228GPa, and the coefficient of variation of the tensile modulus was 2.67%.
[ example 5 ]
After the polyacrylonitrile precursor is uncoiled, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 210 ℃ plus the temperature of 180-; the tensile modulus was 245GPa, and the coefficient of variation of the tensile modulus was 1.55%.
[ example 6 ]
After the polyacrylonitrile precursor is uncoiled, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 200 ℃ at 170-; the tensile modulus was 251GPa, and the coefficient of variation of the tensile modulus was 0.68%.
[ example 7 ]
After the polyacrylonitrile precursor is uncoiled, pre-oxidation is carried out in the air atmosphere, three pre-oxidation furnaces are provided, the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 190 ℃ for 170-; the tensile modulus was 232GPa, and the coefficient of variation of the tensile modulus was 1.21%.
[ COMPARATIVE EXAMPLE 1 ]
After the polyacrylonitrile precursor is uncoiled, pre-oxidation is carried out in the air atmosphere, three pre-oxidation furnaces are provided, the temperature in each pre-oxidation furnace is constant, gradient temperature rise is carried out, the temperature of the 1# pre-oxidation furnace is 170, the temperature of the 2# oxidation furnace is 230 ℃, the temperature of the 3# oxidation furnace is 260 ℃, a driving unit of the pre-oxidation furnace is assembled in the pre-oxidation furnace, then low-temperature carbonization is carried out in sequence at the temperature of 300-; the tensile modulus was 225GPa, and the coefficient of variation of the tensile modulus was 2.97%.
[ COMPARATIVE EXAMPLE 2 ]
After decoiling polyacrylonitrile precursor, carrying out preoxidation in the air atmosphere, wherein the temperature in each preoxidation furnace is constant, carrying out gradient temperature rise, the temperature in the 1# preoxidation furnace is 175 ℃, the temperature in the 2# oxidation furnace is 195 ℃, the temperature in the 3# oxidation furnace is 235 ℃, the temperature in the 4# oxidation furnace is 255 ℃, a preoxidation furnace driving unit is assembled in the preoxidation furnace, then carrying out low-temperature carbonization at 800 ℃ under inert gas in sequence, carrying out high-temperature carbonization at 1500 ℃ under 900 ℃,. finally, winding to obtain carbon fiber, the tensile strength of the carbon fiber is 3264MPa, and the dispersion coefficient of the tensile strength is 6.76%; the tensile modulus was 225GPa, and the modulus of variation of the tensile modulus was 4.88%.
[ COMPARATIVE EXAMPLE 3 ]
After uncoiling polyacrylonitrile precursor, carrying out pre-oxidation in the air atmosphere, wherein the temperature in each pre-oxidation furnace is constant, carrying out gradient temperature rise, the temperature in the 1# pre-oxidation furnace is 170 ℃, the temperature in the 2# oxidation furnace is 200 ℃, the temperature in the 3# oxidation furnace is 230 ℃, the temperature in the 4# oxidation furnace is 260 ℃, a driving unit of the pre-oxidation furnace is assembled in the pre-oxidation furnace, then carrying out low-temperature carbonization at 800 ℃ under inert gas in sequence, carrying out high-temperature carbonization at 1500 ℃ under 900 ℃,. finally, winding to obtain carbon fiber, the tensile strength of the carbon fiber is 3421MPa, and the dispersion coefficient of the tensile strength is 5.92%; the tensile modulus was 229GPa, and the modulus of variation of the tensile modulus was 4.76%.
[ COMPARATIVE EXAMPLE 4 ]
After decoiling polyacrylonitrile precursor, carrying out preoxidation in the air atmosphere, wherein the temperature in each preoxidation furnace is constant, carrying out gradient temperature rise, the temperature in the 1# preoxidation furnace is 170 ℃, the temperature in the 2# oxidation furnace is 200 ℃, the temperature in the 3# oxidation furnace is 230 ℃, the temperature in the 4# oxidation furnace is 260 ℃, a preoxidation furnace driving unit is assembled outside the preoxidation furnace, then carrying out low-temperature carbonization at 800 ℃ under inert gas in sequence, carrying out high-temperature carbonization at 1500 ℃ under 900 ℃ and finally carrying out rolling to obtain carbon fiber, the tensile strength of the carbon fiber is 3325MPa, and the dispersion coefficient of the tensile strength is 6.31%; the tensile modulus was 228GPa, and the coefficient of variation of the tensile modulus was 5.22%.
[ COMPARATIVE EXAMPLE 5 ]
After the polyacrylonitrile precursor is uncoiled, pre-oxidation is carried out in the air atmosphere, four pre-oxidation furnaces are provided, the temperature in each pre-oxidation furnace is continuously changed and gradually increased along the fiber running direction, the temperature of the 1# pre-oxidation furnace is 175-; the tensile modulus was 226GPa, and the coefficient of variation of the tensile modulus was 2.36%.
Obviously, the process and the equipment can achieve the purpose of improving the mechanical property of the carbon fiber, have greater technical advantages and can be used in the industrial production of the carbon fiber.
Claims (9)
1. A pre-oxidation device for improving mechanical properties of carbon fibers comprises the following units: the device comprises a plurality of pre-oxidation furnaces and a driving unit, wherein each pre-oxidation furnace comprises a furnace tube, a heating wire, a heat insulation layer and a shell; the method is characterized in that heating wires in the pre-oxidation furnace are non-uniformly wound on a furnace tube, and the winding density is increased along the wire moving direction, so that the temperature difference from the inlet to the outlet of the pre-oxidation furnace can be 10-50 ℃; the outer surface of the heating wire winding layer on the surface of the furnace tube is provided with a heat preservation layer with the thickness of 20-200cm, and the outer surface of the heat preservation layer is provided with a shell; the driving unit is assembled inside the pre-oxidation furnace; the initial temperature of the latter pre-oxidation furnace is equal to the final temperature of the former pre-oxidation furnace.
2. The pre-oxidation equipment for improving the mechanical property of the carbon fibers according to claim 1, wherein the furnace tube is a stainless steel furnace tube, the heating wire is a nichrome wire, the heat insulation layer is a rock wool heat insulation layer, and the shell is a stainless steel shell.
3. The pre-oxidation equipment for improving the mechanical property of the carbon fiber according to claim 2, wherein the nichrome wire is electrically heated.
4. The pre-oxidation equipment for improving the mechanical property of the carbon fiber according to claim 1, wherein the number of the pre-oxidation furnaces is at least 3, the effective heating length of the pre-oxidation furnaces is 2-6m, and the pre-oxidation fiber is conveyed in the pre-oxidation furnaces through a driving unit.
5. A method for improving mechanical properties of carbon fibers adopts the pre-oxidation equipment as claimed in any one of claims 1 to 4, and sequentially comprises the following steps: the method is characterized in that the pre-oxidation temperature in the pre-oxidation furnace is 180-plus-260 ℃, and the temperature is gradually and continuously increased along the filament moving direction.
6. The method for improving the mechanical property of the carbon fiber according to claim 5, wherein the effective heating time of the pre-oxidized fiber in the pre-oxidation furnace is 45-120 min.
7. The method for improving the mechanical properties of carbon fibers according to claim 5, wherein the number of the pre-oxidation furnaces is at least 3, the temperature of the first pre-oxidation furnace is 180-200 ℃, positive draft is applied to the fibers in the furnace through a driving unit, and the draft ratio is 0 to + 8%; the temperature of the middle pre-oxidation furnace is 230-250 ℃, and zero drafting is applied through a driving unit; and the temperature of the last pre-oxidation furnace is 260-280 ℃, negative drafting is applied through a driving unit, and the drafting ratio is-8% -0.
8. The method for improving mechanical properties of carbon fibers according to claim 5, wherein the driving unit is installed inside the pre-oxidation furnace.
9. The method for improving the mechanical property of the carbon fiber as claimed in claim 5, wherein the pre-oxidized precursor is sequentially carbonized at a low temperature of 300-800 ℃ under an inert atmosphere and carbonized at a high temperature of 800-1500 ℃ under an inert atmosphere.
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CN110106584B (en) * | 2019-04-26 | 2021-11-30 | 全球能源互联网研究院有限公司 | Pre-oxidized fiber and preparation method thereof |
CN112708968B (en) * | 2019-10-24 | 2022-11-04 | 中国石油化工股份有限公司 | Rapid pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
CN110846744A (en) * | 2019-12-18 | 2020-02-28 | 河南永煤碳纤维有限公司 | Method for regulating and controlling homogenization of carbon fiber pre-oxidized fiber and pre-oxidation furnace |
CN116377619A (en) * | 2023-06-05 | 2023-07-04 | 吉林国兴碳纤维有限公司 | 35-50K carbon fiber, preparation method thereof and pre-oxidation furnace for producing 35-50K carbon fiber |
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CN102704043A (en) * | 2012-06-20 | 2012-10-03 | 北京化工大学 | Preparation method of polyacrylonitrile pre-oxidation fiber and carbon fiber |
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CN101260575A (en) * | 2008-04-17 | 2008-09-10 | 东华大学 | Pre-oxidation method for carbon fiber precursor polyacrylnitrile fiber |
CN102704043A (en) * | 2012-06-20 | 2012-10-03 | 北京化工大学 | Preparation method of polyacrylonitrile pre-oxidation fiber and carbon fiber |
CN105568432A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Device and method for producing low-dispersion coefficient carbon fibers |
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