CN114262496A - Preparation method of carbon fiber resin matrix composite material for umbrella ribs - Google Patents
Preparation method of carbon fiber resin matrix composite material for umbrella ribs Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 87
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011159 matrix material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000003763 carbonization Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims description 20
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- BCNCKJAYWXWHDQ-UHFFFAOYSA-N ethanol;ethyl prop-2-enoate Chemical compound CCO.CCOC(=O)C=C BCNCKJAYWXWHDQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000002166 wet spinning Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical group [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 description 45
- 238000005345 coagulation Methods 0.000 description 45
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 238000005452 bending Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- 239000011592 zinc chloride Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IGEPRZISHXJLEO-UHFFFAOYSA-N ethanol;phthalic acid Chemical compound CCO.OC(=O)C1=CC=CC=C1C(O)=O IGEPRZISHXJLEO-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Abstract
The invention relates to the technical field of composite materials, and provides a preparation method of a carbon fiber resin matrix composite material for umbrella ribs, which comprises the following steps: s1, preparing a polyacrylonitrile-based copolymer; s2, preparing polyacrylonitrile-based protofilament; s3, dipping polyacrylonitrile-based protofilament in an ethanol solution of phthalic acid for 30-60 min; s4, pre-oxidation treatment; s5, carbonizing; s6, carrying out acidification treatment for 3-5 h; s7, modifying the surface of the carbon fiber; and S8, compression molding. The invention realizes the application of the carbon fiber resin matrix composite material on the umbrella rib, and solves the problems that the prior carbon fiber and resin interface has weak cohesiveness and is difficult to prepare products with excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a carbon fiber resin matrix composite material for umbrella ribs.
Background
With the development of science and technology, the umbrella is also continuously new, and the umbrella is changed from the oil paper umbrella in the old age to various and various umbrellas at present. The umbrella rib is an important component structure of the umbrella and can be divided into resin ribs, aluminum alloy ribs, iron ribs, glass fiber ribs and the like according to the material. The iron bone is hard and not easy to break, has good wind resistance, but is easy to rust for a long time; the aluminum alloy bone and the resin bone are relatively light and portable, but are easy to bend and break when encountering strong wind or other external forces. The glass fiber umbrella rib has the advantages of good insulation, strong heat resistance, good corrosion resistance, high tensile strength and light weight, but the structural strength is not good, so that the glass fiber umbrella rib cannot bear larger stress, particularly, in the structural configuration of the umbrella, the umbrella ribs at different positions must bear different forces, for example, the umbrella ribs must bear the tension of umbrella cloth to support the ribs, and then the proper axial pushing force must be provided. In addition, the preparation of the glass fiber has the problems of glass crystallization, high strand linear density, high cost and the like.
The carbon fiber is an inorganic fiber material with carbon content of more than 90 percent, and has excellent performances of high specific strength, high specific modulus, low density, high temperature resistance, corrosion resistance and the like. As a high-performance fiber material, carbon fiber has inherent properties of carbon materials, has flexibility and processability of fiber materials, is known as a most vital novel material in the 21 st century, and is widely applied to a plurality of fields such as sports equipment, medical instruments, transportation, aerospace and the like. Although the carbon fiber has the advantages, the carbon fiber is difficult to use alone, and the composite material is required to be prepared to make up the defects of each component and improve the performance of each part. The carbon fiber composite material takes carbon fibers as a reinforcement, and the matrix comprises: resin, metal, ceramic, carbon, or the like. Chinese patent application No.: 201910626968.8 discloses a method for preparing a carbon fiber composite umbrella rib, which comprises the following raw materials: the carbon fiber composite material umbrella rib is characterized by comprising carbon fibers, aluminum, copper, lanthanum, silicon, iron, germanium, yttrium, tin and cobalt, wherein the carbon fibers are matched with the aluminum, other metals are added for matching, the simple substances of the aluminum and the other metals mainly play a strengthening role, the yttrium is added for strengthening the oxidation resistance and the ductility of the umbrella rib and increasing the tensile strength of the umbrella rib, and the germanium, the tin and the cobalt are added for strengthening the strength of the umbrella rib, so that the prepared carbon fiber composite material umbrella rib has higher tensile strength, specific elastic modulus and fatigue strength.
Carbon fiber resin-based composite materials have many excellent characteristics, but the application to the production of umbrella ribs is rarely reported. In addition, the carbon fibers have low surface energy and lack chemically active groups, so that the interfacial adhesion between the carbon fibers and the resin matrix is weak, and it is difficult to efficiently transfer a load. Therefore, the excellent characteristics of the carbon fiber can not be exerted, the overall performance of the composite material is improved, and the mechanical property of the composite material is greatly weakened.
Disclosure of Invention
Therefore, aiming at the content, the invention provides a preparation method of a carbon fiber resin matrix composite material for umbrella ribs, which solves the problems that the existing carbon fiber and resin interface has weak cohesiveness and the umbrella ribs with excellent mechanical property are difficult to prepare.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a carbon fiber resin matrix composite material for umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, a monomer A and a monomer B into a reaction device, stirring and mixing uniformly, adding a reducing agent and an oxidizing agent, carrying out polymerization reaction under nitrogen atmosphere, pouring the obtained product into deionized water after the reaction is finished to terminate the polymerization reaction, carrying out vacuum filtration and washing for many times, filtering, and drying to obtain the polyacrylonitrile-based copolymer;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1-3 hours at the temperature of 60-80 ℃, then sending the mixture into a vacuum drying oven, standing and defoaming for 6-8 hours to obtain a spinning stock solution with the solid content of 12-18%, and carrying out a wet spinning process on the spinning stock solution to obtain polyacrylonitrile-based precursor;
s3, immersing the polyacrylonitrile-based protofilament into an ethanol solution with the concentration of 10-20% of phthalic acid, immersing for 30-60 min, taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor for 10-30 min in a nitrogen atmosphere at 160-180 ℃, then sequentially passing through No. 1-4 temperature zones under an air condition, and carrying out pre-oxidation treatment to obtain pre-oxidized fibers, wherein the temperature of each temperature zone is 205-215 ℃, 235-245 ℃, 255-265 ℃ and 270-280 ℃, and the pre-oxidation time of each temperature zone is 18-25 min, 12-18 min and 8-16 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
s6, mixing the carbon fibers with concentrated nitric acid, acidizing for 3-5 h at the temperature of 65-75 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2-4 hours at 70-80 ℃ to enable the surface of the carbon fibers to be attached with a finishing agent, taking out and drying;
and S8, carrying out compression molding on the surface-modified carbon fiber, resin and a curing agent to obtain the carbon fiber resin matrix composite.
The further improvement is that: the monomer A is any one of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate; the monomer B is any one of methacrylic acid, acrylic acid or itaconic acid.
The further improvement is that: the oxidant is persulfate, and the reducing agent is sodium ascorbate or 1, 3-propane diamine.
The further improvement is that: based on 100 parts by mass of acrylonitrile, the dosage of the monomer A is 2.5-4.5 parts, the dosage of the monomer B is 0.8-1.2 parts, the dosage of deionized water is 300-400 parts, the dosage of a reducing agent is 0.2-0.4 part, and the dosage of an oxidizing agent is 0.2-0.6 part.
The further improvement is that: in S1, the polymerization temperature is 56-60 ℃, and the reaction time is 4-6 h.
The further improvement is that: the wet spinning process comprises the following steps: multi-stage solidification forming, boiling water drawing, water washing, oiling, drying densification, steam drawing and heat setting.
The further improvement is that: the diameter of the polyacrylonitrile-based protofilament is 9-15 mu m.
The further improvement is that: and in the S5, the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, the total time of the low-temperature carbonization is 120-150S, 4 temperature zones are arranged in the low-temperature carbonization stage, the temperature of each temperature zone is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 100-120S, 4 temperature zones are arranged in the high-temperature carbonization stage, and the temperature of each temperature zone is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃.
The further improvement is that: the finishing liquor in S7 was prepared as follows:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, then slowly dropwise adding an ethyl acrylate ethanol solution, stirring and reacting at the temperature of 30-40 ℃ for 20-30 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1: 6-8;
adding another certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of the intermediate product A, stirring and reacting at the temperature of 38-42 ℃ for 20-30 hours, carrying out reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4-6: 1;
dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3-6% of the mass of the high molecular compound B, and stirring and mixing uniformly to obtain finishing liquid.
The further improvement is that: the resin is epoxy resin.
By adopting the technical scheme, the invention has the beneficial effects that:
the carbon fiber resin matrix composite material is applied to the preparation of umbrella rib materials, the characteristics of high performance of carbon fibers and low cost of resin materials are fully utilized, and the portability, the corrosion resistance, the wind resistance and the durability of the umbrella are realized.
The quality of the precursor is one of the key factors influencing the quality of the carbon fiber, and the copolymerization composition, compactness, fineness, crystallization, orientation degree, structural uniformity and other structural characteristics and various defects of the precursor determine the performance of the final carbon fiber to a great extent. The raw silk with high orientation, high strength, good thermal stability, uniform fineness, and less impurities and defects is prepared by optimizing the raw material components and the process parameters of the polyacrylonitrile-based raw silk.
The excellent mechanical property of the polyacrylonitrile-based carbon fiber is determined by the structure of the polyacrylonitrile-based carbon fiber, and the mechanical property of the carbon fiber is seriously influenced by the existence of a skin-core structure. The sheath-core structure is mainly formed gradually in the pre-oxidation process, and the precursor with the diameter of 9-15 mu m is prepared by optimizing the technological parameters of wet spinning, so that the sheath-core structure in the pre-oxidation process can be eliminated to a certain extent, carbonization is promoted, and the fiber structure is converted into a disordered-layer graphite structure. In the pre-oxidation process, the molecular chain has violent thermal motion, the chain segment or chain link has serious disorientation, and more conformations appear, so that the molecular chain is in a thermodynamic stable state. Molecular chain disorientation can directly influence the skin-core structure, so that the polyacrylonitrile-based precursor is firstly soaked in an ethanol solution of phthalic acid before preoxidation, phthalic acid can form phthalic anhydride in the preoxidation process, the dipole effect among cyano groups is reduced, the orientation degree is improved, and the skin-core structure is eliminated. Meanwhile, the presence of phthalic anhydride can also enhance the mechanical properties of the carbon fibers. The nitrogen pretreatment before the pre-oxidation can also improve the skin-core structure of the fiber in the pre-oxidation process.
The carbon fiber is subjected to surface modification, a long-chain macromolecular compound is grafted, a large number of active groups are introduced into the surface of the carbon fiber, the carbon fiber and a resin matrix generate a chemical bonding effect, and the interfacial adhesion between the carbon fiber and the resin is improved, so that the mechanical property of the composite material is improved. The macromolecular compound B prepared by the method has a branched structure, can be diffused into a resin molecular chain to form a physical and chemical entanglement effect, and enhances the interface strength between carbon fibers and resin. The gamma- (methacryloyloxy) propyl trimethoxy silane which can react with the resin is added into the finishing liquid in a proper amount, so that the crosslinking between the carbon fiber and the resin is promoted, and the interface bonding strength between the carbon fiber and the resin is further enhanced at present.
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
Example 1
A preparation method of a carbon fiber resin matrix composite material for umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, methyl acrylate and methacrylic acid into a reaction device, stirring and mixing uniformly, adding sodium ascorbate and ammonium persulfate, carrying out polymerization reaction under a nitrogen atmosphere at the reaction temperature of 56 ℃ for 6h, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, carrying out vacuum filtration and washing for multiple times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
based on 100 parts by mass of acrylonitrile, the using amount of methyl acrylate is 2.5 parts, the using amount of methacrylic acid is 1 part, the using amount of deionized water is 300 parts, the using amount of sodium ascorbate is 0.2 part, and the using amount of ammonium persulfate is 0.2 part;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1h at 60 ℃, then sending the obtained product into a vacuum drying oven, standing and defoaming for 6h to obtain a spinning stock solution with the solid content of 12%, spraying the spinning stock solution through spinneret holes, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a 60% zinc chloride aqueous solution, the coagulation time is 2min, and the coagulation drafting magnification is 2.0; then the mixture enters a second coagulation bath, the temperature of the second coagulation bath is 30 ℃, the second coagulation bath adopts 40% zinc chloride aqueous solution, the coagulation time is 1.5min, the coagulation drawing ratio is 1.0, and then the mixture enters a third coagulation bath, the temperature of the third coagulation bath is 25 ℃, the second coagulation bath adopts 20% zinc chloride aqueous solution, the coagulation time is 1min, and the coagulation drawing ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃, wherein the drawing multiplying power is 6.0, washing with hot water after drawing, the water washing drawing multiplying power is 0.99, then applying silicone oil, drying and densifying through a hot roller, the densifying temperature is 120 ℃, the densifying drawing multiplying power is 0.98, feeding the dried and densified fiber into a superheated steam environment at 145 ℃ for secondary drawing, the drawing multiplying power is 2.5, and finally performing heat setting at 155 ℃ to obtain polyacrylonitrile-based precursor with the diameter of 9 microns;
s3, immersing the polyacrylonitrile-based protofilament in 10% phthalic acid ethanol solution, immersing for 60min, taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor for 10min in a nitrogen atmosphere at 180 ℃, then sequentially passing through No. 1-4 temperature zones under an air condition, and carrying out pre-oxidation treatment to obtain pre-oxidized fibers, wherein the temperature of each temperature zone is 205 ℃, 235 ℃, 255 ℃ and 270 ℃, and the pre-oxidation time of each temperature zone is 18min, 12min and 8 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, the total time of the low-temperature carbonization is 120s, 4 temperature zones are arranged in the low-temperature carbonization stage, the temperature of each temperature zone is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 100s, 4 temperature zones are arranged in the high-temperature carbonization stage, and the temperature of each temperature zone is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, carrying out acidification treatment for 3h at the temperature of 65 ℃, and then placing in a drying oven for drying;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 4 hours at 70 ℃ to enable the surface of the carbon fibers to be attached with a finishing agent, taking out and drying;
the finishing liquid is prepared by the following method:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, then slowly dropwise adding an ethyl acrylate ethanol solution, stirring and reacting at the temperature of 30 ℃ for 20 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1: 6;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, slowly dropwise adding an ethanol solution of the intermediate product A, stirring and reacting at 38 ℃ for 20 hours, carrying out reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4: 1;
dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3% of the mass of the high molecular compound B, and stirring and mixing uniformly to obtain a finishing liquid;
s8, preparing epoxy resin and a curing agent into prepreg resin according to the mass ratio of 2:1, uniformly coating the prepreg resin on release paper on a prepreg machine to prepare a resin film, stretching the surface-modified carbon fibers by a stretching device of the prepreg machine, and laminating the surface-modified carbon fibers and the prepreg resin under the pressure action of a hot press roller to prepare prepreg; cutting the obtained prepreg into a proper size, laying the prepreg in a forming die, forming and curing the prepreg under a molding press, setting the heating temperature of the die to be 180 ℃ and the pressure to be 5MPa, and demolding and cutting the prepreg into the carbon fiber resin matrix composite material for the umbrella ribs after forming.
The carbon fiber resin-based composite material prepared in this example was tested for flexural strength, flexural modulus and interfacial shear strength. The bending strength and the bending modulus are tested according to GB/T1449-2005, and the results show that the carbon fiber resin matrix composite material prepared by the embodiment has the bending strength of 1.75GPa and the bending modulus of 162 GPa. The interfacial shear strength was measured using a universal tester (Instron5667, Instron Inc., USA) at a loading rate of 0.5 μm/s, and the interfacial shear strength of the carbon fiber resin-based composite material prepared in this example was 58.1 MPa.
Example 2
A preparation method of a carbon fiber resin matrix composite material for umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, ethyl acrylate and acrylic acid into a reaction device, stirring and mixing uniformly, adding 1, 3-propane diamine and ammonium persulfate, carrying out polymerization reaction at the reaction temperature of 58 ℃ for 5h in a nitrogen atmosphere, pouring the obtained product into the deionized water after the reaction is finished to terminate the polymerization reaction, carrying out vacuum filtration and washing for multiple times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
based on 100 parts by mass of acrylonitrile, the using amount of ethyl acrylate is 3.5 parts, the using amount of acrylic acid is 0.8 part, the using amount of deionized water is 350 parts, the using amount of 1, 3-propane diamine is 0.3 part, and the using amount of ammonium persulfate is 0.4 part;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 2 hours at 70 ℃, then sending the obtained product into a vacuum drying oven, standing and defoaming for 7 hours to obtain a spinning stock solution with the solid content of 15%, spraying the spinning stock solution through spinneret holes, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a 60% zinc chloride aqueous solution, the coagulation time is 2 minutes, and the coagulation drafting magnification is 2.0; then the mixture enters a second coagulation bath, the temperature of the second coagulation bath is 30 ℃, the second coagulation bath adopts 40% zinc chloride aqueous solution, the coagulation time is 1.5min, the coagulation drawing ratio is 1.0, and then the mixture enters a third coagulation bath, the temperature of the third coagulation bath is 25 ℃, the second coagulation bath adopts 20% zinc chloride aqueous solution, the coagulation time is 1min, and the coagulation drawing ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃, wherein the drawing multiplying power is 5.0, washing with hot water after drawing, the water washing drawing multiplying power is 0.99, then applying silicone oil, drying and densifying through a hot roller, the densifying temperature is 120 ℃, the densifying drawing multiplying power is 0.98, feeding the dried and densified fiber into a superheated steam environment at 145 ℃ for secondary drawing, the drawing multiplying power is 2.0, and finally performing heat setting at 155 ℃ to obtain polyacrylonitrile-based precursor with the diameter of 15 mu m;
s3, immersing polyacrylonitrile-based protofilament in 15% phthalic acid ethanol solution, taking out and drying after immersing for 45min,
s4, heating the dried polyacrylonitrile-based precursor for 20min in a nitrogen atmosphere at the temperature of 170 ℃, then sequentially passing through No. 1-4 temperature zones under the air condition, and carrying out pre-oxidation treatment to obtain pre-oxidized fibers, wherein the temperature of each temperature zone is 210 ℃, 240 ℃, 260 ℃ and 275 ℃, and the pre-oxidation time of each temperature zone is 22min, 15min, 16min and 12 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, the total time of the low-temperature carbonization is 135s, 4 temperature zones are arranged in the low-temperature carbonization stage, the temperature of each temperature zone is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 110s, 4 temperature zones are arranged in the high-temperature carbonization stage, and the temperature of each temperature zone is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, carrying out acidification treatment for 4 hours at the temperature of 70 ℃, and then placing in a drying oven for drying;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 3 hours at 75 ℃ to enable the surface of the carbon fibers to be attached with a finishing agent, taking out and drying;
the finishing liquid is prepared by the following method:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, then slowly dropwise adding an ethyl acrylate ethanol solution, stirring and reacting at the temperature of 35 ℃ for 25 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1: 7;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, slowly dropwise adding an ethanol solution of the intermediate product A, stirring and reacting at the temperature of 40 ℃ for 25 hours, carrying out reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 5: 1;
dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 5% of the mass of the high molecular compound B, and stirring and mixing uniformly to obtain a finishing liquid;
and S8, carrying out compression molding on the surface-modified carbon fiber, epoxy resin and a curing agent to obtain the carbon fiber resin matrix composite.
The carbon fiber resin matrix composite material prepared in the embodiment has the bending strength of 1.79GPa, the bending modulus of 164GPa and the interface shear strength of 61.5 MPa.
Example 3
A preparation method of a carbon fiber resin matrix composite material for umbrella ribs comprises the following steps:
s1, adding deionized water, acrylonitrile, methyl methacrylate and itaconic acid into a reaction device, stirring and mixing uniformly, adding 1, 3-propane diamine and potassium persulfate, carrying out polymerization reaction at 60 ℃ in a nitrogen atmosphere, reacting for 4 hours, pouring the obtained product into deionized water after the reaction is finished to terminate the polymerization reaction, carrying out vacuum filtration and washing for multiple times, and drying after filtration to obtain the polyacrylonitrile-based copolymer;
based on 100 parts by mass of acrylonitrile, the using amount of methyl methacrylate is 4.5 parts, the using amount of itaconic acid is 1.2 parts, the using amount of deionized water is 400 parts, the using amount of 1, 3-propane diamine is 0.4 part, and the using amount of potassium persulfate is 0.6 part;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 3 hours at 80 ℃, then sending the obtained product into a vacuum drying oven, standing and defoaming for 8 hours to obtain a spinning stock solution with the solid content of 18%, spraying the spinning stock solution through spinneret holes, and entering a first coagulation bath, wherein the temperature of the first coagulation bath is 40 ℃, the first coagulation bath adopts a 60% zinc chloride aqueous solution, the coagulation time is 2 minutes, and the coagulation drafting magnification is 2.0; then the mixture enters a second coagulation bath, the temperature of the second coagulation bath is 30 ℃, the second coagulation bath adopts 40% zinc chloride aqueous solution, the coagulation time is 1.5min, the coagulation drawing ratio is 1.0, and then the mixture enters a third coagulation bath, the temperature of the third coagulation bath is 25 ℃, the second coagulation bath adopts 20% zinc chloride aqueous solution, the coagulation time is 1min, and the coagulation drawing ratio is 1.0; drawing the solidified fiber in boiling water at 100 ℃, wherein the drawing multiplying power is 4.0, washing with hot water after drawing, the water washing drawing multiplying power is 0.99, then applying silicone oil, drying and densifying through a hot roller, the densifying temperature is 120 ℃, the densifying drawing multiplying power is 0.98, feeding the dried and densified fiber into a superheated steam environment at 145 ℃ for secondary drawing, the drawing multiplying power is 3.0, and finally performing heat setting at 155 ℃ to obtain polyacrylonitrile-based precursor with the diameter of 12 mu m;
s3, immersing the polyacrylonitrile-based protofilament in 20% phthalic acid ethanol solution, taking out and drying after 30min of immersion,
s4, heating the dried polyacrylonitrile-based precursor for 30min in a nitrogen atmosphere at 160 ℃, then sequentially passing through No. 1-4 temperature zones under an air condition, and carrying out pre-oxidation treatment to obtain pre-oxidized fibers, wherein the temperature of each temperature zone is 215 ℃, 245 ℃, 265 ℃ and 280 ℃, and the pre-oxidation time of each temperature zone is 25min, 18min and 16 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, the total time of the low-temperature carbonization is 150s, 4 temperature zones are arranged in the low-temperature carbonization stage, the temperature of each temperature zone is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 120s, 4 temperature zones are arranged in the high-temperature carbonization stage, and the temperature of each temperature zone is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃;
s6, mixing the carbon fiber with concentrated nitric acid, carrying out acidification treatment for 5h at the temperature of 75 ℃, and then placing in a drying oven for drying;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2 hours at 80 ℃ to enable the surface of the carbon fibers to be attached with a finishing agent, taking out and drying;
the finishing liquid is prepared by the following method:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, then slowly dropwise adding an ethyl acrylate ethanol solution, stirring and reacting at the temperature of 40 ℃ for 30 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1: 8;
adding a certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, slowly dropwise adding an ethanol solution of the intermediate product A, stirring and reacting at 42 ℃ for 30 hours, carrying out reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 6: 1;
dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 6% of the mass of the high molecular compound B, and stirring and mixing uniformly to obtain a finishing liquid;
and S8, carrying out compression molding on the surface-modified carbon fiber, epoxy resin and a curing agent to obtain the carbon fiber resin matrix composite.
The carbon fiber resin matrix composite material prepared in the embodiment has the bending strength of 1.76GPa, the bending modulus of 161GPa and the interface shear strength of 60.6 MPa.
The resin used in the present invention may be, in addition to the above-mentioned epoxy resin, phenol resin, polyether sulfone, polyphenylene sulfide, polyether ether ketone, polyether imide and polyimide.
Comparative example 1
The difference from example 1 is that: step S3 is omitted, and the other steps are the same as in embodiment 1.
The bending strength of the prepared carbon fiber resin matrix composite material is 1.56GPa, the bending modulus is 147GPa, and the interfacial shear strength is 55.4 MPa.
Comparative example 2
The difference from example 1 is that: steps S6 and S7 are omitted, and the other steps are the same as in embodiment 1.
The bending strength of the prepared carbon fiber resin matrix composite material is 1.32GPa, the bending modulus is 125GPa, and the interface shear strength is 51.9 MPa.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (10)
1. A preparation method of a carbon fiber resin matrix composite material for umbrella ribs is characterized by comprising the following steps: the method comprises the following steps:
s1, adding deionized water, acrylonitrile, a monomer A and a monomer B into a reaction device, stirring and mixing uniformly, adding a reducing agent and an oxidizing agent, carrying out polymerization reaction under nitrogen atmosphere, pouring the obtained product into deionized water after the reaction is finished to terminate the polymerization reaction, carrying out vacuum filtration and washing for many times, filtering, and drying to obtain the polyacrylonitrile-based copolymer;
s2, adding the polyacrylonitrile-based copolymer into a dimethyl sulfoxide solvent, stirring and dissolving for 1-3 hours at the temperature of 60-80 ℃, then sending the mixture into a vacuum drying oven, standing and defoaming for 6-8 hours to obtain a spinning stock solution with the solid content of 12-18%, and carrying out a wet spinning process on the spinning stock solution to obtain polyacrylonitrile-based precursor;
s3, immersing the polyacrylonitrile-based protofilament into an ethanol solution with the concentration of 10-20% of phthalic acid, immersing for 30-60 min, taking out and drying;
s4, heating the dried polyacrylonitrile-based precursor for 10-30 min in a nitrogen atmosphere at 160-180 ℃, then sequentially passing through No. 1-4 temperature zones under an air condition, and carrying out pre-oxidation treatment to obtain pre-oxidized fibers, wherein the temperature of each temperature zone is 205-215 ℃, 235-245 ℃, 255-265 ℃ and 270-280 ℃, and the pre-oxidation time of each temperature zone is 18-25 min, 12-18 min and 8-16 min;
s5, carbonizing the pre-oxidized fiber under the protection of inert atmosphere to obtain carbon fiber;
s6, mixing the carbon fibers with concentrated nitric acid, acidizing for 3-5 h at the temperature of 65-75 ℃, and then drying in an oven;
s7, putting the dried carbon fibers into the finishing liquid, stirring for 2-4 hours at 70-80 ℃ to enable the surface of the carbon fibers to be attached with a finishing agent, taking out and drying;
and S8, carrying out compression molding on the surface-modified carbon fiber, resin and a curing agent to obtain the carbon fiber resin matrix composite.
2. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the monomer A is any one of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate; the monomer B is any one of methacrylic acid, acrylic acid or itaconic acid.
3. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the oxidant is persulfate, and the reducing agent is sodium ascorbate or 1, 3-propane diamine.
4. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: based on 100 parts by mass of acrylonitrile, the dosage of the monomer A is 2.5-4.5 parts, the dosage of the monomer B is 0.8-1.2 parts, the dosage of deionized water is 300-400 parts, the dosage of a reducing agent is 0.2-0.4 part, and the dosage of an oxidizing agent is 0.2-0.6 part.
5. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: in S1, the polymerization temperature is 56-60 ℃, and the reaction time is 4-6 h.
6. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the wet spinning process comprises the following steps: multi-stage solidification forming, boiling water drawing, water washing, oiling, drying densification, steam drawing and heat setting.
7. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the diameter of the polyacrylonitrile-based protofilament is 9-15 mu m.
8. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: and in the S5, the carbonization treatment comprises low-temperature carbonization and high-temperature carbonization, the total time of the low-temperature carbonization is 120-150S, 4 temperature zones are arranged in the low-temperature carbonization stage, the temperature of each temperature zone is 450 ℃, 600 ℃, 700 ℃ and 780 ℃, the total time of the high-temperature carbonization is 100-120S, 4 temperature zones are arranged in the high-temperature carbonization stage, and the temperature of each temperature zone is 850 ℃, 1090 ℃, 1300 ℃ and 1500 ℃.
9. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the finishing liquor in S7 was prepared as follows:
adding 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the reaction kettle, then slowly dropwise adding an ethyl acrylate ethanol solution, stirring and reacting at the temperature of 30-40 ℃ for 20-30 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain an intermediate product A, wherein the mass ratio of the 3-dimethylaminopropylamine to the ethyl acrylate is 1: 6-8;
adding another certain amount of 3-dimethylaminopropylamine into a reaction kettle, introducing nitrogen to remove air in the kettle, slowly dropwise adding an ethanol solution of the intermediate product A, stirring and reacting at the temperature of 38-42 ℃ for 20-30 hours, carrying out reduced pressure distillation after the reaction is finished, and purifying to obtain a high molecular compound B with a branched structure, wherein the mass ratio of the 3-dimethylaminopropylamine to the intermediate product A is 4-6: 1;
dissolving the high molecular compound B in an organic solvent, adding gamma- (methacryloyloxy) propyl trimethoxy silane accounting for 3-6% of the mass of the high molecular compound B, and stirring and mixing uniformly to obtain finishing liquid.
10. The preparation method of the carbon fiber resin matrix composite material for the umbrella ribs as claimed in claim 1, which is characterized in that: the resin is epoxy resin.
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