CN114687010B - High-strength high-modulus high-elongation carbon fiber and preparation method thereof - Google Patents
High-strength high-modulus high-elongation carbon fiber and preparation method thereof Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 97
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 97
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002243 precursor Substances 0.000 claims abstract description 61
- 238000009987 spinning Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000009998 heat setting Methods 0.000 claims abstract description 19
- 238000005087 graphitization Methods 0.000 claims abstract description 12
- 238000002166 wet spinning Methods 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 claims description 2
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- -1 amine styrenesulfonate Chemical class 0.000 claims description 2
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 claims description 2
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 claims description 2
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 36
- 238000000280 densification Methods 0.000 description 19
- 208000012886 Vertigo Diseases 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 230000001112 coagulating effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000012258 stirred mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000019771 cognition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 238000003379 elimination reaction Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to the technical field of carbon fiber preparation, and discloses a high-strength high-modulus high-elongation carbon fiber and a preparation method thereof. The method comprises the following steps: step 1, polymerizing acrylonitrile and comonomer solution to obtain spinning solution; step 2, adopting wet spinning, solidifying, washing, hot water drafting, oiling and drying the spinning solution, and then carrying out steam drafting and heat setting to obtain precursor fibers with boiling water shrinkage of 5.0-6.8%, elongation at break of 9.5-11.0% and tensile strength of 4.7-5.9 cN/dtex; and 3, preparing the precursor fiber by pre-oxidation, low-temperature carbonization, high-temperature carbonization and ultrahigh-temperature graphitization to obtain the carbon fiber with the tensile strength of more than or equal to 5.00GPa, the tensile modulus of more than or equal to 540GPa and the elongation at break of more than or equal to 0.90%, wherein the carbon fiber has excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of carbon fiber preparation, in particular to a high-strength high-modulus high-elongation carbon fiber and a preparation method thereof.
Background
The Polyacrylonitrile (PAN) based carbon fiber has the advantages of high tensile strength, high tensile modulus, small thermal expansion coefficient, corrosion resistance, conductivity and the like, so that the Polyacrylonitrile (PAN) based carbon fiber is widely applied to the fields of aerospace, engineering application, civil leisure and the like. The PAN-based carbon fibers can be classified into general-purpose grades (e.g., toril T300 modulus 230 GPa), high-strength medium-modulus grades (e.g., toril T800 modulus 294 GPa), and high-strength high-modulus grades (e.g., toril M55J modulus 540 GPa) according to the tensile modulus of the fibers. The PAN-based high-strength medium-modulus carbon fiber is prepared by preparing PAN precursor fiber (namely PAN precursor fiber), pre-oxidizing, carbonizing at low temperature and carbonizing at high temperature, wherein the high-strength high-modulus carbon fiber is obtained by further carrying out ultrahigh-temperature graphitization treatment at 2000-3000 ℃ on the basis of the high-strength medium-modulus carbon fiber.
The preparation of the high-strength high-modulus carbon fiber is very harsh, and certain strength loss is caused by high-temperature heat treatment in the preparation process, so that the tensile strength of the high-strength high-modulus carbon fiber is generally lower, for example, although the tensile modulus of the Japanese east M55J carbon fiber is as high as 540GPa, the tensile strength of the high-strength high-modulus carbon fiber is only 4.02GPa, and the elongation at break of the high-strength high-modulus carbon fiber is only 0.70%, so that the high-strength high-modulus carbon fiber has the characteristic of low elongation. Because the high-strength high-modulus carbon fiber has the characteristics of low extension and high brittleness, broken filaments and the like are extremely easy to form in the processing process of subsequent products such as prepreg and the like, thereby influencing the quality of the final product. In recent years, the preparation technology of the high-modulus carbon fiber with the tensile modulus of more than 540GPa is gradually broken through in China, but the tensile strength of the product is less than 5.00GPa, and the low extension characteristic limits the further wide application of the product.
In the process of spinning the PAN precursor fiber, in order to eliminate the thermal stress in the fiber and make the thermodynamics of the PAN precursor fiber in a stable state, namely, to obtain the PAN precursor fiber with stable size, the PAN precursor fiber must be subjected to relaxation heat setting treatment, wherein the relaxation heat setting treatment is usually related to hot water drawing, steam drawing and the like, and the boiling water shrinkage rate of the PAN precursor fiber is a key index for representing the heat setting degree of the fiber in the spinning process. In the preparation of high strength medium modulus carbon fibers, the boiling water shrinkage of the PAN precursor fiber is typically 3-4%, and values in the range of this range are generally considered to be better heat set, while values in the range of 6-7% are considered to be worse heat set.
The invention discloses a preparation method of PAN-based high-modulus carbon fiber precursor fiber, wherein the PAN-based high-modulus carbon fiber precursor is prepared by adopting the preparation method, and the preparation method comprises the steps of carrying out hot water drawing multiplying power 2-3 times and steam drawing multiplying power 1.5-2.5 times in the spinning stage of the PAN precursor fiber, and obtaining the PAN precursor fiber with the tensile strength of 7-8cN/dtex and the elongation at break of 12% because the fiber is optimally oriented after heat setting due to the high hot water drawing multiplying power, wherein the tensile modulus is lower than 480GPa although the tensile strength of the carbon fiber prepared by adopting the precursor fiber is higher.
The invention discloses a polyacrylonitrile precursor with high orientation degree for obtaining high-strength high-modulus carbon fiber, a preparation method and application thereof, wherein the steam draft ratio of the precursor fiber in the PAN spinning stage is more up to 3.0-7.0 times, and the tensile modulus of the carbon fiber prepared by using the precursor fiber is only 378GPa-387 GPa due to high hot water draft ratio.
The Chinese patent document of application number 201510581367.1 discloses a preparation method of PAN precursor fiber, a spinning solution with stable performance is obtained through accurate control of a polymerization section, high-quality PAN precursor fiber is obtained under a later stable spinning process, and the precursor fiber has high breaking elongation and strength although the boiling water shrinkage rate is 5.0-6.0 percent, and finally the carbon fiber has a tensile modulus of less than 500GPa through a carbonization graphitization process.
Therefore, it is found that the preparation of high-strength high-modulus carbon fibers and the improvement of the tensile strength and elongation of the carbon fibers cannot always be achieved simultaneously.
Disclosure of Invention
Aiming at the situation that the tensile strength and the elongation at break of the high-strength high-modulus carbon fiber in the prior art are insufficient, or the tensile modulus is difficult to reach very high after the tensile strength and the elongation at break are improved, the invention provides the preparation method of the high-strength high-modulus and high-elongation carbon fiber, the obtained carbon fiber can keep the tensile modulus above 540GPa, the tensile strength of the carbon fiber is greatly improved to above 5.00GPa, and meanwhile, the elongation at break is higher than 0.90%, and the comprehensive performance is very excellent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A preparation method of high-strength high-modulus high-elongation carbon fiber comprises the following steps:
step 1, polymerizing acrylonitrile and comonomer solution to obtain spinning solution;
step 2, adopting wet spinning, solidifying, washing, hot water drafting, oiling and drying the spinning solution, and then carrying out steam drafting and heat setting to obtain precursor fibers;
step 3, preparing the precursor fiber into the high-strength high-modulus high-elongation carbon fiber through pre-oxidation, low-temperature carbonization, high-temperature carbonization and ultrahigh-temperature graphitization;
The precursor fiber has a boiling water shrinkage of 5.0-6.8%, an elongation at break of 9.5-11.0% and a tensile strength of 4.7-5.9cN/dtex.
In the prior art, the common recognition is that the precursor fiber with low boiling water shrinkage (3-4%), high elongation and high strength is beneficial to preparing the high-performance carbon fiber, but the tensile strength of the obtained carbon fiber with high modulus of more than 540GPa is often lower, for example, the strength of the carbon fiber with high modulus of more than 540GPa is only 4.02GPa, or the tensile strength and the elongation at break are improved, but the modulus is reduced, and the carbon fiber with high modulus of more than 540GPa cannot be obtained at all.
In the invention, the research finds that if the high-strength high-modulus high-elongation carbon fiber is to be obtained, the boiling water shrinkage rate of the PAN precursor fiber is required to be higher than 3-4% and controlled to be 5.0-6.8%, which breaks the conventional cognition of the prior art for preparing the carbon fiber, because precursor fibers exceeding the value are generally considered to be poor in heat setting, and the preparation of the high-performance carbon fiber in the later period is not facilitated.
In order to obtain the high-modulus high-strength high-elongation carbon fiber, the elongation at break and the tensile strength of the precursor fiber are controlled within specific ranges, and the properties of the carbon fiber obtained when the elongation at break is 9.5-11.0% and the tensile strength is 4.7-5.9cN/dtex are better comprehensively.
The solvent used in step 1 comprises one or a mixture of DMSO, DMF, DMAC, naSCN, znCl 2、HNO3;
The step 1 also comprises an initiator, wherein the mass of the initiator is 0.1-3wt% of the total mass of the acrylonitrile and the comonomer. Preferably 0.8 to 1.9wt%.
The initiator is a common initiator in the art including, but not limited to, at least one of azobisisobutyronitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile, or dibenzoyl peroxide.
The mass fraction of the polymer in the spinning solution is 15-25wt%.
The comonomer comprises any one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, itaconic acid, beta-ammonium itaconate, monomethyl itaconate, monobutyl itaconate, monoamide itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, acrylamide, methacrylamide, amine styrenesulfonate and the like.
The weight ratio of the acrylonitrile to the comonomer is 97-99:1-3. The introduction of the copolymer component can improve the spinnability of the polymer and help the cyclization of the molecular chain of the precursor fiber, but the monomer is not too high or too low, and the content is low, so that the effect cannot be exerted; too high a content tends to result in an increase in side chain volume and a decrease in carbonization yield, resulting in a decrease in final fiber strength, and the fiber strength obtained in this range is better.
The solidification temperature is 40-85 ℃, preferably 50-65 ℃; the higher solidification temperature is conducive to the increase of diffusion coefficients of the solvent and the coagulant, and macromolecules are easy to orient along the drawing direction, so that a quasi-ordered structure is formed.
The washing temperature is 60-90 ℃, preferably 65-80 ℃; an increase in the water washing temperature contributes to diffusion of the solvent into water, but an excessively high temperature causes an increase in heat consumption and solvent damage, and in this range, the effect is more excellent.
The drying temperature is 120-180 ℃, preferably 130-150 ℃. The drying temperature is controlled to help the densification of the structure and the reduction of the internal stress of the fiber; too low a drying temperature is unfavorable for densification of the fibers, too high a drying temperature leads to a change in the chemical structure of the fibers, and is prone to generation of fuzzing and decrease in the strength of the fibers.
The draft ratio of the hot water draft is 1.0 to 2.0 times, preferably 1.3 to 1.8 times. Hot water drawing can cause relative slippage of amorphous region chains and chain segments, thereby contributing to the increase of fiber crystal region and overall structural orientation.
The steam drafting temperature is 110-150 ℃, preferably 120-135 ℃; the high steam drafting temperature is beneficial to the macromolecular chain segment movement of precursor fibers and the elimination of internal stress in the fibers, and is beneficial to the increase of the strength and the elongation at break of the fibers.
The steam draft ratio is 1.5 to 2.4 times, preferably 1.9 to 2.2 times. Vapor draw contributes to increased density and structural densification, but greater draw ratios result in a concomitant decrease in precursor fiber crystallinity and grain size.
The pre-oxidation process adopts gradient heating treatment in six temperature areas, and the temperature range is 180-260 ℃; the low-temperature carbonization adopts five-temperature-zone gradient heating treatment, and the temperature range is 300-800 ℃; the high-temperature carbonization adopts three-temperature-zone gradient heating treatment, and the temperature range is 1000-1500 ℃; and carrying out heat treatment in an ultra-high temperature graphitization single-temperature zone, wherein the highest temperature is 2800 ℃.
The invention simultaneously realizes the high tensile strength, high tensile modulus and high elongation of the carbon fiber, needs the accurate control of copolymerization components in a polymerization stage, and the matching design of drawing process parameters in the spinning process of the precursor fiber, realizes the regulation and control of the comprehensive performance of PAN precursor fiber by low-power drawing, high-temperature steam drawing and instantaneous heat setting treatment, ensures that the boiling water shrinkage of the precursor fiber is 5.0-6.8%, the elongation at break is 9.5-11.0% and the tensile strength is 4.7-5.9cN/dtex, and can obtain the carbon fiber with the tensile strength of more than or equal to 5.00GPa, the tensile modulus of more than or equal to 540GPa and the elongation at break of more than or equal to 0.90% through pre-oxidation, low-temperature carbonization, high-temperature carbonization and ultrahigh-temperature graphitization in the later stage.
The invention also provides the high-strength high-modulus high-elongation carbon fiber prepared by the preparation method, wherein the tensile strength is more than or equal to 5.00GPa, the tensile modulus is more than or equal to 540GPa, and the elongation at break is more than or equal to 0.90%.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the technological parameters are comprehensively adjusted through a spinning stage, and PAN precursor fibers with boiling water shrinkage of 5.0-6.8%, elongation at break of 9.5-11.0% and tensile strength of 4.7-5.9cN/dtex are obtained through low-power drawing, high-temperature steam drawing and instantaneous heat setting treatment, so that the concept that the heat setting of the precursor with boiling water shrinkage exceeding 3-4% in the traditional cognition is poor is broken, and the carbon fibers obtained through pre-oxidation, carbonization and graphitization have tensile modulus not lower than 540GPa and tensile strength not lower than 5.00GPa, have elongation at break not lower than 0.90%, solve the problem that the high modulus, the high tensile strength and the high elongation performance are not compatible, and obtain the high-modulus high-strength high-elongation carbon fibers with excellent comprehensive performance.
Drawings
FIG. 1 is a drawing curve of a high-strength high-modulus carbon fiber prepared in comparative example 1.
Fig. 2 is a drawing curve of the high-strength high-modulus carbon fiber prepared in comparative example 2.
Fig. 3 is a drawing curve of the high-strength high-modulus carbon fiber prepared in comparative example 3.
Fig. 4 is a drawing curve of the high-strength high-modulus carbon fiber prepared in comparative example 4.
Fig. 5 is a drawing curve of the high-strength, high-modulus, high-elongation carbon fiber prepared in example 1.
Fig. 6 is a drawing curve of the high-strength, high-modulus, high-elongation carbon fiber prepared in example 2.
Fig. 7 is a drawing curve of the high-strength, high-modulus, high-elongation carbon fiber prepared in example 3.
Fig. 8 is a drawing curve of the high-strength, high-modulus, high-elongation carbon fiber prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Comparative example 1
(1) Preparing spinning solution:
And (3) taking DMSO as a solvent and azodiisobutyl cyanide as an initiator, wherein the weight ratio of acrylonitrile to itaconic acid is 96.5:3.5, stirring uniformly in a batching kettle, adding the stirred mixture into a polymerization kettle, performing solution polymerization in the polymerization kettle at the polymerization temperature of 63 ℃ for intermittent polymerization for 20 hours, and obtaining the spinning stock solution with the polymer concentration of 23 percent after removing monomers and defoaming.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 65 ℃; hot water draft ratio is 1.3 times; and (3) drying densification temperature 140 ℃, and carrying out 2.0 times steam drafting at 130 ℃ to prepare the PAN precursor fiber.
The resulting precursor fiber had a boiling water shrinkage of 6.74%, an elongation at break of 13.12% and a tensile strength of 6.04cN/dtex.
(3) Preparation of high-strength high-modulus carbon fiber
Taking the PAN precursor fiber as a raw material, performing air pre-oxidation treatment at 180-260 ℃, performing low-temperature carbonization treatment at 300-800 ℃ under nitrogen atmosphere, performing high-temperature carbonization treatment at 1000-1500 ℃ under nitrogen atmosphere, and performing ultrahigh-temperature graphitization treatment at 2700 ℃ under argon atmosphere to obtain the carbon fiber.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 1, the tensile curve is shown in figure 1, and the average value is obtained to obtain the carbon fiber with the tensile strength of 3.99GPa, the tensile modulus of 516GPa and the elongation of 0.77%.
TABLE 1 tensile Properties of high-strength high-modulus carbon fiber
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 4.08 | 513 | 0.8 |
| 2 | 4.08 | 525 | 0.78 |
| 3 | 3.72 | 521 | 0.71 |
| 4 | 3.94 | 510 | 0.77 |
| 5 | 4.07 | 522 | 0.78 |
| 6 | 3.85 | 508 | 0.76 |
| 7 | 4.16 | 507 | 0.82 |
| 8 | 4.06 | 519 | 0.78 |
| Mean value of | 3.99 | 516 | 0.77 |
| Coefficient of variation | 3.66 | 1.36 | 3.94 |
Comparative example 2
(1) Preparing spinning solution:
And (3) taking DMSO as a solvent and azodiisobutyl cyanide as an initiator, wherein the weight ratio of acrylonitrile to acrylic acid is 99.0:1.0, stirring uniformly in a batching kettle, adding the stirred mixture into a polymerization kettle, performing solution polymerization in the polymerization kettle at the polymerization temperature of 65 ℃ for 20 hours, and obtaining the spinning stock solution with the polymer concentration of 22 percent after removing monomers and defoaming.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 65 ℃; hot water draft ratio is 2.2 times; and (3) drying densification temperature is 140 ℃, and 2.6 times of steam drafting is carried out at the temperature of 120 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 6.52%, an elongation at break of 11.2% and a tensile strength of 6.58cN/dtex.
The procedure and parameters of step (3) were the same as those of comparative example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 2, the tensile curve is shown in figure 2, and the average value is obtained to obtain the carbon fiber with the tensile strength of 4.77GPa, the tensile modulus of 545GPa and the elongation of 0.87%.
TABLE 2 tensile Properties of high-strength high-modulus carbon fibers
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 4.82 | 548 | 4.82 |
| 2 | 4.86 | 542 | 4.86 |
| 3 | 4.74 | 553 | 4.74 |
| 4 | 4.90 | 544 | 4.90 |
| 5 | 4.74 | 554 | 4.74 |
| 6 | 4.62 | 543 | 4.62 |
| 7 | 4.60 | 541 | 4.60 |
| 8 | 4.86 | 539 | 4.86 |
| Mean value of | 4.77 | 545 | 4.77 |
| Coefficient of variation | 2.33 | 1.03 | 2.33 |
Comparative example 3
The procedure and parameters of step (1) are the same as those of example 2
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; the hot water draft ratio is 3.0 times; and (3) drying densification temperature is 140 ℃, and 2.8 times of steam drafting is carried out at the temperature of 100 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 6.22%, an elongation at break of 12.0% and a tensile strength of 6.72cN/dtex.
The procedure and parameters of step (3) were the same as those of comparative example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 3, the tensile curve is shown in figure 3, and the average value is obtained to obtain the carbon fiber with 4.08GPa, 551GPa and 0.74% of elongation.
TABLE 3 tensile Properties of high strength and high modulus carbon fiber
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 4.27 | 560 | 0.76 |
| 2 | 4.08 | 559 | 0.73 |
| 3 | 4.11 | 549 | 0.75 |
| 4 | 4.28 | 545 | 0.78 |
| 5 | 3.78 | 545 | 0.69 |
| 6 | 4.12 | 558 | 0.74 |
| 7 | 4.15 | 550 | 0.75 |
| 8 | 3.88 | 545 | 0.71 |
| Mean value of | 4.08 | 551 | 0.74 |
| Coefficient of variation | 4.29 | 1.21 | 3.91 |
Comparative example 4
The procedure and parameters of step (1) are the same as those of example 2
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; hot water draft ratio is 2.0 times; drying densification temperature is 150 ℃, and 4.5 times of steam drafting is carried out at 165 ℃ to prepare PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 5.22%, an elongation at break of 13.1% and a tensile strength of 7.62cN/dtex.
The procedure and parameters of step (3) were the same as those of comparative example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 4, the tensile curve is shown in fig. 4, and the average value is obtained to obtain the carbon fiber with the tensile strength of 5.16GPa, the tensile modulus of 485GPa and the elongation of 1.06%.
TABLE 4 tensile Properties of high-strength high-modulus carbon fibers
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 5.08 | 474 | 1.07 |
| 2 | 5.32 | 480 | 1.11 |
| 3 | 5.11 | 499 | 1.02 |
| 4 | 4.92 | 478 | 1.03 |
| 5 | 5.17 | 485 | 1.07 |
| 6 | 5.12 | 493 | 1.04 |
| 7 | 5.30 | 474 | 1.12 |
| 8 | 5.26 | 498 | 1.06 |
| Mean value of | 5.16 | 485 | 1.06 |
| Coefficient of variation | 2.57 | 2.16 | 3.26 |
Example 1
The preparation method of the high-strength high-modulus high-elongation carbon fiber comprises the following steps:
(1) Preparing spinning solution:
And (3) taking DMSO as a solvent and azodiisobutyl cyanide as an initiator, wherein the weight ratio of acrylonitrile to itaconic acid is 99.5:0.5, stirring uniformly in a batching kettle, adding the stirred mixture into a polymerization kettle, performing solution polymerization in the polymerization kettle at the polymerization temperature of 65 ℃ for intermittent polymerization for 20 hours, and obtaining the spinning stock solution with the polymer concentration of 20 percent after removing monomers and defoaming.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; hot water draft ratio is 1.4 times; and (3) drying densification temperature is 140 ℃, and 2.0 times of steam drafting is carried out at the temperature of 120 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 5.45%, an elongation at break of 10.10% and a tensile strength of 5.10cN/dtex.
(3) Preparation of high-strength high-modulus high-elongation carbon fiber
Taking the PAN precursor fiber as a raw material, performing air pre-oxidation treatment at 180-260 ℃, performing low-temperature carbonization treatment at 300-800 ℃ under nitrogen atmosphere, performing high-temperature carbonization treatment at 1000-1500 ℃ under nitrogen atmosphere, and performing ultrahigh-temperature graphitization treatment at 2700 ℃ under argon atmosphere to obtain the carbon fiber.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 5, the tensile curve is shown in figure 5, and the average value is obtained to obtain the carbon fiber with the tensile strength of 5.06GPa, the tensile modulus of 550GPa and the elongation of 0.92%.
TABLE 5 tensile Properties of high strength, high modulus, high elongation carbon fiber
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 5.08 | 544 | 0.93 |
| 2 | 5.17 | 554 | 0.93 |
| 3 | 5.07 | 553 | 0.92 |
| 4 | 5.00 | 542 | 0.92 |
| 5 | 5.14 | 545 | 0.94 |
| 6 | 4.98 | 548 | 0.91 |
| 7 | 5.09 | 540 | 0.94 |
| 8 | 4.98 | 574 | 0.87 |
| Mean value of | 5.06 | 550 | 0.92 |
| Coefficient of variation | 1.50 | 2.00 | 2.70 |
Example 2
The preparation method of the high-strength high-modulus carbon fiber comprises the following steps:
the procedure and parameters of step (1) were the same as in example 1.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; the hot water draft ratio is 1.5 times; and (3) drying densification temperature 140 ℃, and carrying out 2.1 times steam drafting at 130 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 5.64%, an elongation at break of 10.52% and a tensile strength of 5.34cN/dtex.
The procedure and parameters of step (3) were the same as in example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 6, the tensile curve is shown in figure 6, and the average value is obtained to obtain the carbon fiber with the tensile strength of 5.08GPa, the tensile modulus of 545GPa and the elongation of 0.93%.
TABLE 6 tensile Properties of high strength, high modulus, high elongation carbon fiber
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 5.16 | 532 | 0.97 |
| 2 | 4.73 | 555 | 0.85 |
| 3 | 4.87 | 545 | 0.89 |
| 4 | 5.10 | 536 | 0.95 |
| 5 | 5.21 | 567 | 0.92 |
| 6 | 5.10 | 531 | 0.96 |
| 7 | 5.29 | 556 | 0.95 |
| 8 | 5.14 | 537 | 0.96 |
| Mean value of | 5.08 | 545 | 0.93 |
| Coefficient of variation | 3.60 | 2.40 | 4.40 |
Example 3
The preparation method of the high-strength high-modulus carbon fiber comprises the following steps:
the procedure and parameters of step (1) were the same as in example 1.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; the hot water draft ratio is 1.5 times; and (3) drying densification temperature is 140 ℃, and 2.0 times of steam drafting is carried out at the temperature of 120 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 5.20%, an elongation at break of 10.57% and a tensile strength of 5.32cN/dtex.
The procedure and parameters of step (3) were the same as in example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 7, the tensile curve is shown in figure 7, and the average value is obtained to obtain the carbon fiber with the tensile strength of 5.01GPa, the tensile modulus of 552GPa and the elongation of 0.91%.
TABLE 7 tensile Properties of high strength, high modulus, high elongation carbon fiber
| Sample numbering | Tensile Strength/GPa | Tensile modulus/GPa | Elongation/% |
| 1 | 5.14 | 550 | 0.93 |
| 2 | 4.95 | 559 | 0.89 |
| 3 | 5.28 | 549 | 0.96 |
| 4 | 4.55 | 520 | 0.88 |
| 5 | 5.14 | 578 | 0.89 |
| 6 | 4.94 | 580 | 0.85 |
| 7 | 4.99 | 547 | 0.91 |
| 8 | 5.10 | 533 | 0.96 |
| Mean value of | 5.01 | 552 | 0.91 |
| Coefficient of variation | 4.30 | 3.70 | 4.40 |
Example 4
The preparation method of the high-strength high-modulus carbon fiber comprises the following steps:
the procedure and parameters of step (1) were the same as in example 1.
(2) Wet spinning:
Solidifying the mixture into fibers in DMSO/H 2 O coagulating bath at 55 ℃ by adopting a 6000-hole spinneret plate, and performing water washing, hot water drafting, oiling, drying densification, steam drafting and heat setting, wherein deionized water is adopted for water washing, and the temperature is 70 ℃; hot water draft ratio is 1.4 times; and (3) drying densification temperature is 140 ℃, and 2.0 times of steam drafting is carried out at the temperature of 140 ℃ to prepare the PAN precursor fiber.
The precursor fiber had a boiling water shrinkage of 5.38%, an elongation at break of 10.66% and a tensile strength of 5.30cN/dtex.
The procedure and parameters of step (3) were the same as in example 1.
The fiber performance is detected according to national standard GB-T3362-2005, 8 samples are tested in each group of tests, the data of the 8 samples are shown in the following table 8, the tensile curve is shown in figure 8, and the average value is obtained to obtain the carbon fiber with the tensile strength of 5.03GPa, the tensile modulus of 544GPa and the elongation of 0.93%.
TABLE 8 tensile Properties of high strength high modulus high elongation carbon fiber
Comparative examples 1 and 2 above show the effect of polymerization stage and spinning stage parameter control on the final fiber properties, respectively.
In comparative example 1, the addition amount of the comonomer itaconic acid is large, the itaconic acid contains carboxyl, intramolecular cyclization of polyacrylonitrile can be initiated, the higher content of the itaconic acid leads to increase of cyano cyclization initiation points in a pre-oxidation stage, the cyclization reaction rate is accelerated, a skin-core structure is easy to form, and further the strength of finally obtained carbon fiber is obviously reduced and the modulus is lower.
The higher magnification of hot water drawing and steam drawing in comparative example 2 is conducive to the improvement of the internal orientation and carbonization stage of the fiber, but the high orientation after high temperature graphitization treatment is not conducive to structural rearrangement when non-carbon elements overflow, thereby resulting in the reduction of the strength of the final carbon fiber; the ratio of hot water drawing and steam drawing is further increased in comparative example 3 than in comparative example 2, and the steam drawing temperature is lower, which is disadvantageous for the elimination of the internal stress of the fiber, and the strength of the final carbon fiber is further reduced.
In comparative example 4, the steam drawing temperature was increased to facilitate the increase of the fiber strength and elongation at break, but the crystallinity and grain size of the precursor fiber were decreased as the drawing magnification of the steam drawing was larger, which was disadvantageous for the increase of the modulus at the final graphitization stage, so that the prepared carbon fiber had high strength and high elongation, but the modulus was lower than 500GPa, and the comprehensive properties were still poor.
As can be seen from the observations of examples 1 to 4, the key parameter coupling optimization design is realized from polymerization to spinning in the precursor fiber preparation process, and under the cooperation of the parameters, particularly the regulation and control of the temperature, tension and the like in the spinning stage, the precursor fiber with high boiling water shrinkage, low elongation and strength, which is different from the prior knowledge, is obtained, and based on the precursor fiber, the high-strength high-modulus high-elongation carbon fiber with the tensile modulus of more than 540GPa and the elongation at break of more than 0.90% is prepared through the subsequent heat treatment.
The above embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the high-strength high-modulus high-elongation carbon fiber is characterized by comprising the following steps:
step 1, polymerizing acrylonitrile and comonomer solution to obtain spinning solution;
step 2, adopting wet spinning, solidifying, washing, hot water drafting, oiling and drying the spinning solution, and then carrying out steam drafting and heat setting to obtain precursor fibers;
the solidification temperature is 40-85 ℃; the washing temperature is 60-90 ℃; the drying temperature is 120-180 ℃; the draft ratio of the hot water draft is 1.0-2.0 times; the steam drafting temperature is 110-150 ℃ and the drafting multiplying power is 1.5-2.4 times;
step 3, preparing the precursor fiber into the high-strength high-modulus high-elongation carbon fiber through pre-oxidation, low-temperature carbonization, high-temperature carbonization and ultrahigh-temperature graphitization;
The pre-oxidation process adopts gradient heating treatment in six temperature areas, and the temperature range is 180-260 ℃; the low-temperature carbonization adopts five-temperature-zone gradient heating treatment, and the temperature range is 300-800 ℃; the high-temperature carbonization adopts three-temperature-zone gradient heating treatment, and the temperature range is 1000-1500 ℃; carrying out heat treatment on the ultrahigh-temperature graphitized single-temperature zone, wherein the temperature is 2700-2800 ℃;
the boiling water shrinkage rate of the precursor fiber is 5.0-6.8%, the elongation at break is 9.5-11.0%, and the tensile strength is 4.7-5.9cN/dtex;
The high-strength high-modulus high-elongation carbon fiber has tensile strength more than or equal to 5.00GPa, tensile modulus more than or equal to 540GPa and elongation at break more than or equal to 0.90%.
2. The method for producing high-strength, high-modulus and high-elongation carbon fiber according to claim 1, wherein the solvent used in step 1 comprises one or a mixture of DMSO, DMF, DMAC, naSCN, znCl 2、HNO3.
3. The method for preparing high-strength, high-modulus and high-elongation carbon fiber according to claim 1, further comprising an initiator in the step 1, wherein the mass of the initiator is 0.1-3wt% of the total mass of acrylonitrile and comonomer.
4. The method for preparing high-strength, high-modulus and high-elongation carbon fibers according to claim 1, wherein the mass fraction of the polymer in the spinning solution is 15-25wt%.
5. The method for preparing the high-strength, high-modulus and high-elongation carbon fiber according to claim 1, wherein the comonomer comprises any one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, itaconic acid, beta-ammonium itaconate, monomethyl itaconate, monobutyl itaconate, monoamide itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, acrylamide, methacrylamide and amine styrenesulfonate.
6. The method for preparing high-strength, high-modulus and high-elongation carbon fiber according to claim 1, wherein the weight ratio of acrylonitrile to comonomer is 97-99:1-3.
7. The high-strength high-modulus high-elongation carbon fiber prepared by the preparation method according to any one of claims 1 to 6, wherein the tensile strength is not less than 5.00GPa, the tensile modulus is not less than 540GPa, and the elongation at break is not less than 0.90%.
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