CN109280998A - A kind of preparation method of PAN base high-strength and high-modulus type carbon fiber - Google Patents
A kind of preparation method of PAN base high-strength and high-modulus type carbon fiber Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 59
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000835 fiber Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005087 graphitization Methods 0.000 claims abstract description 36
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002166 wet spinning Methods 0.000 claims abstract description 4
- 238000007743 anodising Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 24
- 238000011282 treatment Methods 0.000 claims description 19
- 238000004381 surface treatment Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000013081 microcrystal Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009955 starching Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- -1 argon ion Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000007380 fibre production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
- D01F9/20—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 present invention relates to carbon fiber manufacturing technology field, specifically a kind of preparation method of PAN base high-strength and high-modulus type carbon fiber prepares 6K polyacrylonitrile fibril using wet spinning mode, uses 6 sections of gradient increased temperature modes that density is made as 1.35 ± 0.02g/cm3Pre-oxidized fibers；Under -2 ~ 2% draw ratio, 2 ± 0.5min of low-temperature carbonization at 300 ~ 900 DEG C；Under -4 ~ 0% draw ratio, at 1000 ~ 1800 DEG C, 3 ± 0.5min is handled through 6 ~ 8 sections of gradient increased temperature high temperature cabonizations；Under 5~10% draw ratio, at 2500 ~ 2800 DEG C, through 5 ~ 7 sections of gradient increased temperature 2 ± 0.5min of high temperature graphitization, graphite fibre is obtained；Gained graphite fibre is surface-treated 2 ± 0.5min through anodizing, obtains modified graphite fiber, and modified graphite fiber handles to obtain PAN base high-strength and high-modulus type carbon fiber using washing, starching.
Description
Technical Field
The invention relates to the technical field of carbon fiber production, in particular to a preparation method of PAN-based high-strength high-model carbon fiber.
Background
As is well known, Polyacrylonitrile (PAN) carbon fibers are classified according to their mechanical properties, and generally classified into four categories, i.e., a high-strength standard model, a high-strength medium model, a high model, and a high-strength high model. The high-strength high-model carbon fiber has the characteristics of light weight, high strength, high modulus and the like, also has the characteristics of high heat conduction, high electric conduction, good dimensional stability, good fatigue performance, good shock resistance and the like, has outstanding environmental alternation resistance and strong environmental adaptability, can be used as a reinforcement to prepare various structural and functional composite materials with high rigidity and high dimensional stability, and is widely applied to the field of aerospace.
The high-strength high-model carbon fibers such as M40J, M46J, M55J and M60J are successively developed by Toho corporation of Japan, and the high-strength high-model carbon fibers such as UMS40, UMS45 and UMS55 are also developed by Toho corporation of Japan, so that the problem of light weight of materials in the field of foreign aerospace is well solved. In recent years, the research and development of domestic high-strength high-model carbon fibers have also made breakthrough progress, and M55J-grade carbon fibers are developed successively by Ningbo materials institute of Chinese academy of sciences, Beijing chemical university and Wighai extended fiber Co., Ltd. Because the tensile modulus of M55J is up to 540GPa, the carbon content is more than 99%, the heat treatment temperature is more than 2500 ℃, the graphitization degree is high, the surface chemical inertness is large, and the bonding with matrix resin is not facilitated. Domestic scholars have conducted a great deal of intensive research on high-strength and high-model carbon fibers, and the research reports on the surface treatment of the high-strength and high-model carbon fibers are few.
The Chinese patent with the application number of 201810113188.9 proposes that high-temperature carbonized fiber with the orientation angle not more than 17.5 degrees is obtained by effectively controlling the orientation of microcrystals, and then high-strength high-model carbon fiber with the tensile strength of 3.8-5.0 GPa and the tensile modulus of 500-600 GPa is prepared at a relatively low high-temperature graphitization temperature, however, the microcrystals parameters and graphitization degree of the carbon fiber are not represented, and the surface activity of the carbon fiber is not improved by surface modification.
In 2017, Tianyanhong et al, in the journal of composite materials journal, namely "domestic polyacrylonitrile-based high-strength high-modulus carbon fiber electrochemical oxidation surface treatment process", the influence of electrochemical oxidation on the surface structure and chemical composition of the high-strength high-modulus carbon fiber is proposed and researched, and the mechanical property of the carbon fiber is represented by testing the interlaminar shear strength after the carbon fiber is combined with resin. Although the electrolyte is screened and the current density is researched, the fiber with certain O/C and N/C ratios is prepared, and the interlaminar shear strength of the fiber is about 60MPa after the fiber is combined with the epoxy 6101. However, the concentration and temperature of the electrolyte solution were not studied, and the surface free energy was not characterized, and the interlaminar shear strength of the bond with the matrix resin was only about 60MPa, which is much lower than 75MPa or more of the method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of PAN-based high-strength high-model carbon fiber, which defines a graphitization treatment method and a surface modification method and quantitatively controls the microcrystalline structure and the surface chemical structure of graphite fiber to prepare the high-strength high-model carbon fiber.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of PAN-based high-strength high-model carbon fiber is characterized by comprising the following steps: the 6K Polyacrylonitrile (PAN) protofilament is prepared by adopting a wet spinning mode, and the density of the precursor is 1.35 +/-0.02 g/cm by adopting a 6-section gradient heating mode3The pre-oxidized fiber of (a); carbonizing at low temperature of 300-900 ℃ for 2 +/-0.5 min under the condition of a draft ratio of-2%; carrying out 6-8 sections of gradient temperature rise high-temperature carbonization treatment for 3 +/-0.5 min at the temperature of 1000-1800 ℃ under the condition of a draw ratio of-4-0%; under the condition of 5-10% of draft ratio and at the temperature of 2500-2800 ℃, carrying out 5-7 stages of gradient temperature rise high-temperature graphitization for 2 +/-0.5 min to obtain graphite fibers; and performing surface treatment on the obtained graphite fiber by an anodic oxidation method for 2 +/-0.5 min to obtain modified graphite fiber, and performing water washing and sizing treatment on the modified graphite fiber to obtain the PAN-based high-strength high-model carbon fiber.
The interlayer spacing of the graphite microcrystals of the graphite fiberd 0020.3430-0.3440 nm, and stacked microcrystalL c10.0 to 16.0nm, degree of graphitizationRLess than or equal to 0.7, and the fiber diameter is 5.2 +/-0.2 mu m.
In the surface treatment process by the anodic oxidation method, the electrolyte is ammonium bicarbonateThe concentration of the weak base is 10 +/-0.5%, the temperature is 30 +/-10 ℃, and the current density is 0.30 +/-0.05 mA/cm2。
The polar component of the surface free energy of the modified graphite fiber is more than or equal to 12.0mN/m, the content of surface active elements O/C is more than or equal to 0.05, and the content of N/C is more than or equal to 0.005.
The method has the beneficial effects that the graphitization treatment method and the surface modification method are defined, and the microcrystalline structure and the surface chemical structure of the graphite fiber are quantitatively controlled, so that the high-strength high-model carbon fiber is prepared, the tensile strength of the high-strength high-model carbon fiber is 4.5-5.0 GPa, the tensile modulus of the high-strength high-model carbon fiber is 540-580 GPa, and the interlaminar shear strength matched with the epoxy resin is more than or equal to 75 MPa. The high-strength high-model carbon fiber with excellent performance can be obtained by controlling the microcrystalline structure and the graphitization degree of the graphite fiber, the interface bonding force between the high-strength high-model carbon fiber and matrix resin can be improved by controlling the polar component of the surface free energy of the graphite fiber and the contents of surface active elements O/C and N/C, and the high-strength high-model carbon fiber has good guiding significance for the application of the high-strength high-model carbon fiber in high-end fields such as aerospace and the like.
Detailed Description
The invention is further described with reference to the following examples:
example 1:
(1) PAN precursor preoxidation
Selecting low-titer 6K PAN precursor produced by Wenhai expanded fiber Limited company through wet spinning, and in an air medium, adopting a 6-section gradient heating mode, wherein the preoxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the retention time is 90min, and the obtained product has the density of 1.35g/cm3The pre-oxidized fiber of (1).
(2) Low temperature carbonization
And carbonizing the obtained pre-oxidized fiber at the temperature of 300-750 ℃ for 2min under the protection of nitrogen, and drawing by + 2%.
(3) High temperature carbonization
And (3) treating the obtained low-temperature carbonized fiber for 3min by adopting a 7-section gradient heating mode under the protection of nitrogen, wherein the high-temperature carbonization starting temperature is 1100 ℃, the highest temperature is 1600 ℃, and applying-3.0% drafting.
(4) Graphitization
And (3) under the protection of argon, treating the obtained high-temperature carbonized fiber for 2min by adopting a 5-section gradient temperature rise mode, wherein the graphitization carbonization starting temperature is 2500 ℃, the highest temperature is 2600 ℃, and applying +8.0% drafting to obtain the graphitization fiber. The graphitized fibers were subjected to the test characterization of the crystallite structure and the graphitization degree by using an X-ray diffractometer and a raman spectrometer (the same below), and the test results are shown in table 1.
(5) Surface treatment
Treating the obtained graphitized fiber with ammonium bicarbonate electrolyte at 35 deg.C for 2min, with electrolyte concentration of 10.0% and current density of 0.30 mA/cm2And obtaining the surface modified graphitized fiber. The surface modified graphite fiber was subjected to surface free energy polarity component and surface active element content test characterization (the same below) using an X-ray photoelectron spectrometer and a DCAT21 surface dynamic contact angle measuring instrument, and the test results are listed in table 1.
(6) Post-treatment
The obtained surface modified graphite fiber is subjected to water washing, drying, sizing, drying and rolling treatment to obtain the high-strength high-model carbon fiber, the carbon fiber performance test is carried out by adopting GB/T3362-.
In the steps, the characterization of the microcrystal parameters is tested by an X-ray diffractometer (XRD), the X-ray source is CuK α, the wavelength is 0.1542nm, and the interlayer spacing of the carbon fiber graphite microcrystal is (d 002) And the stacking dimension (L c) From along the carbon fiberObtained by a Vildahl scan, crystallite length: (L a) Obtained from a meridional scan of the carbon fiber. Layer spacingd 002As calculated from the Bragg's law,d 002=λ/2sinθ. Crystallite sizeL cAndL acalculated by the Scherrer equation, the equation,L=Kλ/βcosθ. Wherein,din order to obtain the interplanar spacing,θin the form of a bragg angle, the angle,λin order to be the wavelength of the incident X-rays,Lis the size of the crystal plane,βis full Width at half maximum (FWHM), from the measured apparent full Width at half maximumBAnd instrumental normal temperaturebAnd calculating to obtain:β 2=（B 2-b 2）），Kfor the geometric factor or shape factor of Xiele, when solvingL cWhen the temperature of the water is higher than the set temperature,Ktake 0.89, when solvingL aWhen the temperature of the water is higher than the set temperature,Ktake 1.84.
In the steps, the graphitization degree is tested by adopting a Raman spectrometer, a light source is an argon ion laser, the wavelength is 532nm, and the Raman frequency range is 0-3300 cm-1，0～1650cm-1Is a first-level ordered area, 1650-3300 cm-1Is a second order region. Wherein the characteristic Raman spectral line corresponds to a wave number D line (D-line) of 1360cm-1The method is a reflection of small microcrystals, low orientation, unsaturated edge, more asymmetric carbon atoms and more structural defects; line G (G-line) is 1580cm-1Can be used for characterizing sp in the graphite structure2The degree of integrity of the hybrid structure. Thus, the integrated area ratio of D line and G lineR=A D/A GThe values may be used to characterize the degree of graphitization and structural integrity of the carbon fiber,Rthe smaller the value, the higher the degree of graphitization of the carbon fiber.
In the steps, the contents of O/C and N/C of surface active elements are tested by an X-ray photoelectron spectrometer, wherein the ray source is MgK α, and the power is 250W.
In the above steps, the surface free energy is tested by using a DCAT21 surface dynamic contact angle measuring instrument, dynamic contact angles of the fiber with water and ethylene glycol are respectively tested, and the fiber surface free energy is calculated based on an OWRK method, wherein the surface free energy is divided into a polar component and a dispersion component, the polar component represents an acting force between polar molecules, and the dispersion component represents an adhesion wetting capability between nonpolar molecules.
In the steps, the interlaminar shear strength is tested according to JC/T773-2010, and epoxy resin AG-80 and 4, 4-diaminodiphenyl sulfone curing systems are selected as test samples. The proportion of the resin and the curing agent is 5:2 (w/w), the resin and the curing agent are mixed and then fully stirred, and the mixture is quickly and uniformly coated on the surface of the carbon fiber, so that the carbon fiber and the resin are fully soaked as much as possible. Putting the carbon fiber coated with the resin into a die for compression molding, wherein the curing system comprises the following steps: 140 ℃/2.5h, 160 ℃/3h and 180 ℃/2.5h, taking out the sample strip, and then manufacturing the CFRP test sample strip according to the standard required size (the span-thickness ratio is 5: 1). The testing instrument INSTRON-3365 type universal material testing machine has the following loading speed: 2 mm/min. The results of each sample test were averaged over 10 valid data sets.
Example 2:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (5) surface treatment, and (6) post-treatment were performed in the same manner as in example 1.
(4) Graphitization
And (3) applying +10.0% drafting at the maximum graphitization temperature of 2600 ℃ to obtain the graphite fiber. The remaining process parameters were the same as in example 1.
The test results are listed in table 1.
Example 3:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (5) surface treatment, and (6) post-treatment were performed in the same manner as in example 1.
(4) Graphitization
The graphitization maximum temperature is 2700 ℃, and +6.0% drafting is applied to obtain the graphite fiber. The remaining process parameters were the same as in example 1.
The test results are listed in table 1.
Comparative example 1:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (5) surface treatment, and (6) post-treatment were performed in the same manner as in example 1.
(4) Graphitization
And (4) applying +8.0% drafting at the maximum graphitization temperature of 2400 ℃ to obtain the graphite fiber. The remaining process parameters were the same as in example 1.
The test results are listed in table 1.
Comparative example 2:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (5) surface treatment, and (6) post-treatment were performed in the same manner as in example 1.
(4) Graphitization
The graphitization highest temperature is 2450 ℃, and the plus 4.0% drafting is applied to obtain the graphite fiber. The remaining process parameters were the same as in example 1.
The test results are listed in table 1.
Example 4:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (4) graphitization, and (6) post-treatment, as in example 1.
(5) Surface treatment
Electrolyte concentration 10.0%, current density 0.28 mA/cm2To obtain the surface modified graphitized fiber, the rest of the processing parameters are the same as those of the example 1.
The test results are listed in table 1.
Example 5:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (4) graphitization, and (6) post-treatment, as in example 1.
(5) Surface treatment
Electrolyte concentration 10.0%, current density 0.33 mA/cm2To obtain the surface modified graphitized fiber, the rest of the processing parameters are the same as those of the example 1.
The test results are listed in table 1.
Comparative example 3:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (4) graphitization, and (6) post-treatment, as in example 1.
(5) Surface treatment
Electrolyte concentration 8.0%, current density 0.20 mA/cm2To obtain the surface modified graphitized fiber, the rest of the processing parameters are the same as those of the example 1.
The test results are listed in table 1.
Comparative example 4:
(1) pre-oxidation of PAN precursor, (2) low-temperature carbonization, (3) high-temperature carbonization, (4) graphitization, and (6) post-treatment, as in example 1.
(5) Surface treatment
Electrolyte concentration 10.0%, current density 0.40 mA/cm2To obtain the surface modified graphitized fiber, the rest of the processing parameters are the same as those of the example 1.
The test results are listed in table 1.
As can be seen from the examples and comparative examples in table 1:
(1) the mechanical property and the interlaminar shear strength of the high-strength high-modulus carbon fiber prepared by the method are superior to those of the Nippon Dongli company.
(2) As can be seen from the microstructures and mechanical properties corresponding to examples 1 to 3 and comparative examples 1 to 2, the crystallite parametersd 002The size of the product is small, and the product is small,L cthe size of the product is small, and the product is small,Rand the prepared high-strength high-model carbon fiber has high mechanical property, and the interlaminar shear strength is basically equivalent under the same surface treatment condition.
(3) As can be seen from the microstructures and the mechanical properties corresponding to examples 1, 4 and 5 and comparative examples 3 to 4, the polar component of the free energy of the fiber surface is large, and the contents of the surface active elements, O/C and N/C, are high, which is beneficial to improving the interlaminar shear strength of the high-strength high-model carbon fiber, however, if the surface treatment degree is too large, the mechanical properties and the interlaminar shear strength of the high-strength high-model carbon fiber are reduced.
The invention defines the graphitization treatment method and the surface modification method, and quantitatively controls the microcrystalline structure and the surface chemical structure of the graphite fiber to prepare the high-strength high-model carbon fiber. The results show that: under the condition of 5-10% of draft ratio, carrying out 5-7 sections of gradient temperature rise high-temperature graphitization for 2 +/-0.5 min to obtain the interlamellar spacing of the graphite microcrystald 0020.3430-0.3440 nm, and stacked microcrystalL c10.0 to 16.0nm, degree of graphitizationRGraphite fiber with fiber diameter of 5.2 +/-0.2 micron not more than 0.7; the obtained graphite fiber is subjected to surface treatment by anodic oxidation method for 2 + -0.5 min, the electrolyte is weak base such as ammonium bicarbonate, the concentration is 10 + -0.5%, the temperature is 30 + -10 deg.C, and the current density is 0.30 + -0.05 mA/cm2Obtaining the modified graphite fiber with the surface free energy of more than or equal to 12.0mN/m, the surface active element content O/C of more than or equal to 0.05 and the N/C of more than or equal to 0.005, and then obtaining the PAN-based high-strength high-model carbon fiber through the treatments of water washing, sizing and the like. The high-strength high-model carbon fiber obtained by the method has the tensile strength of 4.5-5.0 GPa, the tensile modulus of 540-580 GPa, and the interlaminar shear strength matched with the epoxy resin is more than or equal to 75 MPa. By way of example demonstrationThe mechanical properties of the graphite fiber are obviously influenced by controlling the graphitization treatment conditions and controlling the microcrystalline structure and graphitization degree of the graphitized fiber. The polar component of the surface free energy and the contents of surface active elements O/C and N/C are controlled by regulating and controlling the processing conditions such as concentration, temperature, current density and the like in the surface processing process, and the influence on the interface combination between the high-strength high-model carbon fiber and the matrix resin is obvious. Therefore, the high-strength high-model carbon fiber with excellent performance can be obtained by controlling the microcrystalline structure and the graphitization degree of the graphite fiber, the interface bonding force between the high-strength high-model carbon fiber and matrix resin can be improved by controlling the polar component of the surface free energy of the graphite fiber and the contents of surface active elements O/C and N/C, and the high-strength high-model carbon fiber has good guiding significance for the application of the high-strength high-model carbon fiber in high-end fields such as aerospace and the like.
Claims (4)
1. A preparation method of PAN-based high-strength high-model carbon fiber is characterized by comprising the following steps: the 6K polyacrylonitrile protofilament is prepared by adopting a wet spinning mode, and the density of the precursor is 1.35 +/-0.02 g/cm by adopting a 6-section gradient heating mode3The pre-oxidized fiber of (a); carbonizing at low temperature of 300-900 ℃ for 2 +/-0.5 min under the condition of a draft ratio of-2%; carrying out 6-8 sections of gradient temperature rise high-temperature carbonization treatment for 3 +/-0.5 min at the temperature of 1000-1800 ℃ under the condition of a draw ratio of-4-0%; under the condition of 5-10% of draft ratio and at the temperature of 2500-2800 ℃, carrying out 5-7 stages of gradient temperature rise high-temperature graphitization for 2 +/-0.5 min to obtain graphite fibers; the obtained graphite fiberAnd (3) carrying out surface treatment on the fiber for 2 +/-0.5 min by using an anodic oxidation method to obtain modified graphite fiber, and carrying out water washing and sizing treatment on the modified graphite fiber to obtain the PAN-based high-strength high-model carbon fiber.
2. The method for preparing a PAN-based high-strength high-model carbon fiber according to claim 1, wherein the graphite fiber has a graphite crystallite having an interlayer spacing of graphite crystallitesd 0020.3430-0.3440 nm, and stacked microcrystalL c10.0 to 16.0nm, degree of graphitizationRLess than or equal to 0.7, and the fiber diameter is 5.2 +/-0.2 mu m.
3. The method for preparing PAN-based high-strength high-model carbon fiber according to claim 1, wherein in the anodizing surface treatment process, the electrolyte is weak base such as ammonium bicarbonate with a concentration of 10 ± 0.5%, a temperature of 30 ± 10 ℃ and a current density of 0.30 ± 0.05mA/cm2。
4. The method for preparing PAN-based high-strength high-model carbon fiber according to claim 1, wherein the polar component of the surface free energy of the modified graphite fiber is not less than 12.0mN/m, the content of surface active elements O/C is not less than 0.05, and the content of N/C is not less than 0.005.
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| CN110055624A (en) * | 2019-05-20 | 2019-07-26 | 中国科学院山西煤炭化学研究所 | Method for pre-oxidizing, polyacrylonitrile carbon fiber and the preparation method of polyacrylonitrile fibre |
| CN110067044A (en) * | 2019-05-20 | 2019-07-30 | 中国科学院山西煤炭化学研究所 | A kind of PAN based graphite fiber and preparation method thereof |
| CN110396732A (en) * | 2019-08-23 | 2019-11-01 | 大同新成新材料股份有限公司 | A kind of processing technology of modified carbon fiber |
| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
| CN110528264A (en) * | 2019-09-11 | 2019-12-03 | 北京化工大学 | A kind of high modulus carbon fiber and preparation method thereof as thermoplastic resin based composite material reinforcement |
| CN111691011A (en) * | 2020-07-07 | 2020-09-22 | 山西钢科碳材料有限公司 | Polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN113914095A (en) * | 2021-11-25 | 2022-01-11 | 北京化工大学 | Preparation method of PAN-based high-strength high-model carbon fiber with improved interface performance |
| CN113930867A (en) * | 2021-11-19 | 2022-01-14 | 威海拓展纤维有限公司 | Surface modification method of carbon fiber |
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| CN110055624A (en) * | 2019-05-20 | 2019-07-26 | 中国科学院山西煤炭化学研究所 | Method for pre-oxidizing, polyacrylonitrile carbon fiber and the preparation method of polyacrylonitrile fibre |
| CN110067044A (en) * | 2019-05-20 | 2019-07-30 | 中国科学院山西煤炭化学研究所 | A kind of PAN based graphite fiber and preparation method thereof |
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| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
| CN110396732A (en) * | 2019-08-23 | 2019-11-01 | 大同新成新材料股份有限公司 | A kind of processing technology of modified carbon fiber |
| CN110528264A (en) * | 2019-09-11 | 2019-12-03 | 北京化工大学 | A kind of high modulus carbon fiber and preparation method thereof as thermoplastic resin based composite material reinforcement |
| CN111691011A (en) * | 2020-07-07 | 2020-09-22 | 山西钢科碳材料有限公司 | Polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN111691011B (en) * | 2020-07-07 | 2022-11-29 | 山西钢科碳材料有限公司 | Polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN113930867A (en) * | 2021-11-19 | 2022-01-14 | 威海拓展纤维有限公司 | Surface modification method of carbon fiber |
| CN113914095A (en) * | 2021-11-25 | 2022-01-11 | 北京化工大学 | Preparation method of PAN-based high-strength high-model carbon fiber with improved interface performance |
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