CN104233514A - Polyacrylonitrile carbon fiber and preparation method thereof - Google Patents
Polyacrylonitrile carbon fiber and preparation method thereof Download PDFInfo
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- CN104233514A CN104233514A CN201410511578.3A CN201410511578A CN104233514A CN 104233514 A CN104233514 A CN 104233514A CN 201410511578 A CN201410511578 A CN 201410511578A CN 104233514 A CN104233514 A CN 104233514A
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Abstract
The invention discloses polyacrylonitrile carbon fiber and a preparation method thereof. The preparation method comprises the following steps: feeding polyacrylonitrile raw silk into a heating furnace with the temperature of 120-150 DEG C, and performing low-temperature heat treatment for 10-60 days to obtain low-temperature heat treated silk; B, feeding the low-temperature heat treated silk into a continuous preoxidation furnace with the temperature of 220-280 DEG C, and performing continuous preoxidation heat treatment for 20-40 minutes to obtain preoxidized silk; C, feeding the preoxidized silk into a low-temperature carbonization furnace, and performing low-temperature carbonization heat treatment at 350-650 DEG C for 4-20 minutes to obtain preoxidized low-temperature carbonized silk; D, feeding the preoxidized low-temperature carbonized silk into a high-temperature carbonization furnace, and performing high-temperature carbonization heat treatment at 900-1,300 DEG C for 1-2 minutes to obtain the polyacrylonitrile carbon fiber. The preparation method is simple in process and convenient and safe to perform and control, and meets the requirements of batch production.
Description
Technical field
The present invention relates to chemical material field, particularly relate to a kind of polyacrylonitrile carbon fiber and preparation method thereof.
Background technology
Carbon fiber all has wide application in the national economy major fields such as energy industry, civil construction, communications and transportation, ocean engineering and sports entertainment article.High-performance fiber and composite, as new material and strategic material, have become one of development priority of country " 12 " period emerging strategic industries.
Polyacrylonitrile carbon fiber will through a series of heat treatment in the process of preparation, wherein preoxidation process is one of most important step, through preoxidation process, stable heat resistant structure can be obtained, thus reduce the cracking of carbonation stage carbon, to obtain, carbon yield is higher, the carbon fiber of excellent performance.Preoxidation process not only controls the quality of carbon fiber, and also control the output of carbon fiber.Current carbon fiber pre-oxidation process equipment is complicated, energy consumption is high, is the committed step affecting carbon fiber production efficiency, is also carbon fibre producing facility investment the best part.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of polyacrylonitrile carbon fiber and preparation method thereof, be intended to solve existing preparation method's complex process equipment, energy consumption is high, cost is high, inefficient problem.
Technical scheme of the present invention is as follows:
A preparation method for polyacrylonitrile carbon fiber, wherein, comprises step:
A, polyacrylonitrile fibril is sent to 120 ~ 150 DEG C heating furnace in carry out Low Temperature Heat Treatment and obtain Low Temperature Heat Treatment silk, the processing time is 10 ~ 60 days;
B, above-mentioned Low Temperature Heat Treatment silk is sent to 220 ~ 280 DEG C continuous pre-oxidation furnace in carry out continuous pre-oxidation heat treatment and obtain preoxided thread, the processing time is 20 ~ 40min;
C, to be sent in low temperature carbonization furnace by preoxided thread and carry out low-temperature carbonization heat treatment and obtain pre-oxidation low-temperature carbonization silk, treatment temperature is 350 ~ 650 DEG C, and the processing time is 4 ~ 20min;
D, to be entered in high temperature carbonization furnace by pre-oxidation low-temperature carbonization silk and carry out high temperature cabonization heat treatment and obtain polyacrylonitrile carbon fiber, treatment temperature is 900 ~ 1300 DEG C, and the time is 1 ~ 2min.
The preparation method of described polyacrylonitrile carbon fiber, wherein, in described step B, continuous pre-oxidation furnace is provided with 2 ~ 5 warm areas, and continuous pre-oxidation furnace passes into air, and draw ratio is 2 ~ 5%, and tension force is 10 ~ 50MPa.
The preparation method of described polyacrylonitrile carbon fiber, wherein, in described step C, passes into nitrogen in described low temperature carbonization furnace, and draw ratio is 2 ~ 5%, and tension force is 10 ~ 20MPa.
The preparation method of described polyacrylonitrile carbon fiber, wherein, in described step D, passes into nitrogen in described high temperature carbonization furnace, and draw ratio is-4 ~-1%, and tension force is 10 ~ 20MPa.
The preparation method of described polyacrylonitrile carbon fiber, wherein, by mass percentage, polyacrylonitrile carbon fiber phosphorus content obtained in step D is 93 ~ 94%, and volume density is 1.76 ~ 1.80g/cm
3.
The preparation method of described polyacrylonitrile carbon fiber, wherein, in described steps A, passes into air in heating furnace.
The preparation method of described polyacrylonitrile carbon fiber, wherein, described polyacrylonitrile fibril is the fiber of rolling, and containing methyl acrylate and itaconic acid comonomer, tow is 3K or 12K.
The preparation method of described polyacrylonitrile carbon fiber, wherein, in described step B, C and D, the draw ratio when processing is controlled by the wire speed ratio of each stove two ends fiber.
A kind of polyacrylonitrile carbon fiber, wherein, adopts preparation method as above to make.
Beneficial effect: the present invention can under the prerequisite reducing production cost, and preparing TENSILE STRENGTH is 3.69 ~ 3.98GPa, and stretch modulus is the polyacrylonitrile carbon fiber of 232 ~ 248GPa.Production technology of the present invention is simple, convenient operation and control, safe, feasible, meets the requirement of batch production, can increase substantially the production efficiency of present stage carbon fiber.
Accompanying drawing explanation
Fig. 1 is the flow chart of polyacrylonitrile carbon fiber preparation method of the present invention.
Detailed description of the invention
The invention provides a kind of polyacrylonitrile carbon fiber and preparation method thereof, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, Fig. 1 is the flow chart of preparation method's preferred embodiment of a kind of polyacrylonitrile carbon fiber of the present invention, and as shown in the figure, it comprises step:
S101, polyacrylonitrile fibril is sent to 120 ~ 150 DEG C heating furnace in carry out Low Temperature Heat Treatment and obtain Low Temperature Heat Treatment silk, the processing time is 10 ~ 60 days;
S102, above-mentioned Low Temperature Heat Treatment silk is sent to 220 ~ 280 DEG C continuous pre-oxidation furnace in carry out continuous pre-oxidation heat treatment and obtain preoxided thread, the processing time is 20 ~ 40min;
S103, to be sent in low temperature carbonization furnace by preoxided thread and carry out low-temperature carbonization heat treatment and obtain pre-oxidation low-temperature carbonization silk, treatment temperature is 350 ~ 650 DEG C, and the processing time is 4 ~ 20min;
S104, to be entered in high temperature carbonization furnace by pre-oxidation low-temperature carbonization silk and carry out high temperature cabonization heat treatment and obtain polyacrylonitrile carbon fiber, high temperature cabonization carburizing temperature is 900 ~ 1300 DEG C, and the time is 1 ~ 2min.
In the present embodiment, combined by batch (-type) pre-oxidation process and continuous carbonization technique, prepare polyacrylonitrile carbon fiber.Batch (-type) pre-oxidation process is made up of Low Temperature Heat Treatment and continuous pre-oxidation treatment two parts technique.Carbon fibre producing facility investment significantly can be reduced by batch (-type) pre-oxidation process, and Simplified flowsheet, improve carbonization speed and efficiency, reduce energy consumption, the carbon fiber tensile strength prepared by method of the present invention can reach 3.69 ~ 3.98GPa, and stretch modulus can reach 232 ~ 248GPa.
What technique of the present invention was total is divided into four-stage: Low Temperature Heat Treatment, pre-oxidation heat treatment continuously, low-temperature carbonization and high temperature cabonization four-stage, be described this four-stage below respectively.
First in step S101, batch polyacrylonitrile (PAN) precursor is carried out Low Temperature Heat Treatment, the object of Low Temperature Heat Treatment realizes PAN strand intramolecule occurred before disorientation to divide cyclisation, reduce the cracking of PAN strand in follow-up continuous pre-oxidation and carbonisation, shorten follow-up continuous preoxidation time simultaneously, improve pre-oxidation production efficiency, reduce carbon fiber production cost.
Polyacrylonitrile fibril used in the present invention can adopt the fiber of rolling, and containing methyl acrylate and itaconic acid comonomer, tow is 3K(3000 root monofilament number/bundle) or 12K(12000 root monofilament number/bundle).
When carrying out Low Temperature Heat Treatment in heating furnace, stove domestic demand adopts air-blast device to pass into air, and ensure furnace air atmosphere, the color of polyacrylonitrile fibril becomes yellow from white, and heat treatment time is longer, and temperature is higher, then color is darker.The treatment temperature of Low Temperature Heat Treatment is preferably 120 ~ 150 DEG C, and the processing time is preferably 10 ~ 60 days.
Then in step s 102, carry out continuous pre-oxidation heat treatment, owing to carrying out Low Temperature Heat Treatment before, so in this step, Simple process can be realized, change 8 ~ 10 traditional warm areas, only need 2 ~ 5 warm areas, realize rapid preoxidation, improve production efficiency, decrease energy consumption, reduce cost.
In this step, continuous pre-oxidation furnace passes into air, and draw ratio is 2 ~ 5%, and tension force is 10 ~ 50MPa, and temperature is preferably 220 ~ 280 DEG C, and the processing time is 20 ~ 40min.
In step s 103, be sent to by preoxided thread in low temperature carbonization furnace and carry out low-temperature carbonization heat treatment, the heat treated treatment temperature of low-temperature carbonization is preferably 350 ~ 650 DEG C, and the processing time is preferably 4 ~ 20min.And in low temperature carbonization furnace, passing into nitrogen (such as passing into the high pure nitrogen of 99.999%), draw ratio is 2 ~ 5%, and tension force is 10 ~ 20MPa.
In step S104, the low-temperature carbonization silk obtained by step S103 is sent in high temperature carbonization furnace and carries out high temperature cabonization heat treatment, and the heat treated treatment temperature of high temperature cabonization is preferably 900 ~ 1300 DEG C, and the processing time is preferably 1 ~ 2min.And in high temperature carbonization furnace, passing into nitrogen (such as passing into the high pure nitrogen of 99.999%), draw ratio is-4 ~-1%, and tension force is 10 ~ 20MPa.
Last polyacrylonitrile carbon fiber phosphorus content is 93 ~ 94%(mass percent), volume density is 1.76 ~ 1.80g/cm
3.
In continuous pre-oxidation heat treatment in above-mentioned steps, low-temperature carbonization heat treatment, the heat treated step of high temperature cabonization, the draw ratio of each step is controlled by the wire speed ratio of each stove (continuous pre-oxidation furnace, low temperature carbonization furnace or high temperature carbonization furnace) two ends fiber.Continuous pre-oxidation heat treatment and low-temperature carbonization heat treatment stages control positive drawing-off, and high temperature cabonization heat treatment stages controls negative drawing-off, and the tension force applied is controlled by draw ratio.
Under the prerequisite that the present invention can reduce at production cost, preparing TENSILE STRENGTH is 3.69 ~ 3.98GPa, stretch modulus is the polyacrylonitrile carbon fiber of 232 ~ 248GPa, production technology of the present invention simplifies, convenient operation and control, safe, feasible, meet the demand of batch production, significantly can improve the production efficiency of polyacrylonitrile carbon fiber.
Based on said method, the present invention also provides a kind of polyacrylonitrile carbon fiber, and it adopts preparation method as above to make.
Specific embodiment is provided to be specifically described the present invention below.
Embodiment 1
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 120 DEG C, and heat treatment time is 60 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 1%.
Continuous pre-oxidation furnace sets up 3 warm areas separately, is respectively 220,250,270 DEG C, and draw ratio is 3%, and tension force is 15MPa, and total residence time is 25min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 15min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.75GPa, and Young's modulus is 232GPa.
Embodiment 2
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 120 DEG C, and heat treatment time is 60 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 1%.
Continuous pre-oxidation furnace sets up 4 warm areas separately, is respectively 220,240,260,280 DEG C, and draw ratio is 4.5%, and tension force is 20MPa, and total residence time is 35min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 15min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.98GPa, and Young's modulus is 245GPa.
Embodiment 3
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 130 DEG C, and heat treatment time is 30 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 1.5%.
Continuous pre-oxidation furnace sets up 3 warm areas separately, is respectively 220,250,270 DEG C, and draw ratio is 3%, and tension force is 15MPa, and total residence time is 25min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 20min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.81GPa, and Young's modulus is 240GPa.
Embodiment 4
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 130 DEG C, and heat treatment time is 30 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 1%.
Continuous pre-oxidation furnace sets up 4 warm areas separately, is respectively 220,240,260,280 DEG C, and draw ratio is 4.5%, and tension force is 20MPa, and total residence time is 35min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 10min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.85GPa, and Young's modulus is 248GPa.
Embodiment 5
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 140 DEG C, and heat treatment time is 15 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 2.3%.
Continuous pre-oxidation furnace sets up 3 warm areas separately, is respectively 220,250,270 DEG C, and draw ratio is 3%, and tension force is 15MPa, and total residence time is 25min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 15min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.75GPa, and Young's modulus is 239GPa.
Embodiment 6
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 140 DEG C, and heat treatment time is 15 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 2.3%.
Continuous pre-oxidation furnace sets up 4 warm areas separately, is respectively 220,240,260,280 DEG C, and draw ratio is 4.5%, and tension force is 20MPa, and total residence time is 35min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 500,650 DEG C, and total residence time is 15min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.69GPa, and Young's modulus is 238GPa.
Embodiment 7
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 150 DEG C, and heat treatment time is 10 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 2%.
Continuous pre-oxidation furnace sets up 2 warm areas separately, is respectively 230,270 DEG C, and draw ratio is 2%, and tension force is 50MPa, and total residence time is 40min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 350,500 DEG C, and total residence time is 20min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 5%, and tension force is 10MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1300 DEG C, total residence time is 1min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-2%, tension force is 20MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.72GPa, and Young's modulus is 242GPa.
Embodiment 8
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 135 DEG C, and heat treatment time is 40 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 1.5%.
Continuous pre-oxidation furnace sets up 5 warm areas separately, is respectively 220,230,250,270,280 DEG C, and draw ratio is 5%, and tension force is 10MPa, and total residence time is 30min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 400,600 DEG C, and total residence time is 4min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 2%, and tension force is 20MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, high temperature carbonization furnace sets up two warm areas separately, be respectively 900,1200 DEG C, total residence time is 1.5min, the high pure nitrogen of 99.999% is passed in stove, draw ratio is-1%, and tension force is 10MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.83GPa, and Young's modulus is 245GPa.
Embodiment 9
Batch PAN precursor is first carried out Low Temperature Heat Treatment, then carries out continuous pre-oxidation heat treatment, low-temperature carbonization heat treatment and high temperature cabonization heat treatment respectively by continuous pre-oxidation furnace, low temperature carbonization furnace, high temperature carbonization furnace successively.
The temperature of Low Temperature Heat Treatment is 140 DEG C, and heat treatment time is 20 days, and the color of fiber is become faint yellow from white, fiber generating portion intramolecular cyclization reaction.Fiber does not apply drawing-off, and shrinkage factor is 2.5%.
Continuous pre-oxidation furnace sets up 4 warm areas separately, is respectively 220,250,260,270 DEG C, and draw ratio is 4%, and tension force is 35MPa, and total residence time is 35min.Pass into air in stove and promote that the cyclisation of fiber is cross-linked and oxidation reaction, prepare preoxided thread.
Preoxided thread enters in low temperature carbonization furnace, and low temperature carbonization furnace sets up two warm areas separately, is respectively 350,550 DEG C, and total residence time is 4min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is 3.5%, and tension force is 15MPa, obtains PAN pre-oxidation low-temperature carbonization silk.
PAN pre-oxidation low-temperature carbonization silk enters in high temperature carbonization furnace, and high temperature carbonization furnace sets up two warm areas separately, is respectively 900,1200 DEG C, total residence time is 2min, passes into the high pure nitrogen of 99.999% in stove, and draw ratio is-4%, tension force is 15MPa, obtains PAN carbon fiber (polyacrylonitrile-based carbon fibre).
The TENSILE STRENGTH obtaining polyacrylonitrile-based carbon fibre by above-mentioned steps operation is 3.75GPa, and Young's modulus is 238GPa.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (9)
1. a preparation method for polyacrylonitrile carbon fiber, is characterized in that, comprises step:
A, polyacrylonitrile fibril is sent to 120 ~ 150 DEG C heating furnace in carry out Low Temperature Heat Treatment and obtain Low Temperature Heat Treatment silk, the processing time is 10 ~ 60 days;
B, above-mentioned Low Temperature Heat Treatment silk is sent to 220 ~ 280 DEG C continuous pre-oxidation furnace in carry out continuous pre-oxidation heat treatment and obtain preoxided thread, the processing time is 20 ~ 40min;
C, to be sent in low temperature carbonization furnace by preoxided thread and carry out low-temperature carbonization heat treatment and obtain pre-oxidation low-temperature carbonization silk, treatment temperature is 350 ~ 650 DEG C, and the processing time is 4 ~ 20min;
D, to be entered in high temperature carbonization furnace by pre-oxidation low-temperature carbonization silk and carry out high temperature cabonization heat treatment and obtain polyacrylonitrile carbon fiber, treatment temperature is 900 ~ 1300 DEG C, and the time is 1 ~ 2min.
2. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, in described step B, continuous pre-oxidation furnace is provided with 2 ~ 5 warm areas, and continuous pre-oxidation furnace passes into air, and draw ratio is 2 ~ 5%, and tension force is 10 ~ 50MPa.
3. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, in described step C, passes into nitrogen in described low temperature carbonization furnace, and draw ratio is 2 ~ 5%, and tension force is 10 ~ 20MPa.
4. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, in described step D, passes into nitrogen in described high temperature carbonization furnace, and draw ratio is-4 ~-1%, and tension force is 10 ~ 20MPa.
5. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, by mass percentage, polyacrylonitrile carbon fiber phosphorus content obtained in step D is 93 ~ 94%, and volume density is 1.76 ~ 1.80g/cm
3.
6. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, in described steps A, passes into air in heating furnace.
7. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, described polyacrylonitrile fibril is the fiber of rolling, and containing methyl acrylate and itaconic acid comonomer, tow is 3K or 12K.
8. the preparation method of polyacrylonitrile carbon fiber according to claim 1, is characterized in that, in described step B, C and D, the draw ratio when processing is controlled by the wire speed ratio of each stove two ends fiber.
9. a polyacrylonitrile carbon fiber, is characterized in that, adopts the preparation method as described in any one of claim 1 to 9 to make.
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| CN105200566A (en) * | 2015-10-21 | 2015-12-30 | 西北化工研究院 | Method for preparing high-modulus carbon fiber by adopting precursor drawing technology |
| CN108823683A (en) * | 2018-07-06 | 2018-11-16 | 北京化工大学 | Polyacrylonitrile carbon fiber and preparation method thereof |
| CN109722743A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyolefin resin based composites carbon fiber and preparation method thereof |
| CN110655737A (en) * | 2019-10-16 | 2020-01-07 | 厦门欧势复材科技有限公司 | Preparation method of impact-resistant carbon fiber material |
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| CN104790070A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation |
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| CN109722743B (en) * | 2017-10-27 | 2022-02-11 | 中国石油化工股份有限公司 | Carbon fiber for polyolefin resin matrix composite material and preparation method thereof |
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| CN108823683A (en) * | 2018-07-06 | 2018-11-16 | 北京化工大学 | Polyacrylonitrile carbon fiber and preparation method thereof |
| CN112142888A (en) * | 2019-06-26 | 2020-12-29 | 中国科学院山西煤炭化学研究所 | Polyacrylonitrile spinning solution and preparation method thereof |
| CN112142888B (en) * | 2019-06-26 | 2021-08-17 | 中国科学院山西煤炭化学研究所 | Polyacrylonitrile spinning solution and preparation method thereof |
| CN110655737A (en) * | 2019-10-16 | 2020-01-07 | 厦门欧势复材科技有限公司 | Preparation method of impact-resistant carbon fiber material |
| CN112708968A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Rapid pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
| 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 |
| CN110983493A (en) * | 2019-12-28 | 2020-04-10 | 西安康本材料有限公司 | Process for improving carbonization efficiency of PAN-based carbon fiber |
| CN112779664A (en) * | 2020-06-01 | 2021-05-11 | 张家港伟诺复合材料有限公司 | Carbon fiber composite material processing technology and vertical drying device thereof |
| CN112779664B (en) * | 2020-06-01 | 2024-04-16 | 张家港伟诺复合材料有限公司 | Carbon fiber composite material processing technology and vertical drying device thereof |
| CN115323529A (en) * | 2022-09-02 | 2022-11-11 | 山东大学 | System and method for improving preoxidation carbonization efficiency of polyacrylonitrile-based carbon fiber precursor |
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