CN113863001A - Carbon fiber surface complexing modification method - Google Patents
Carbon fiber surface complexing modification method Download PDFInfo
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- CN113863001A CN113863001A CN202111319981.2A CN202111319981A CN113863001A CN 113863001 A CN113863001 A CN 113863001A CN 202111319981 A CN202111319981 A CN 202111319981A CN 113863001 A CN113863001 A CN 113863001A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 80
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 79
- 238000002715 modification method Methods 0.000 title claims abstract description 13
- 230000000536 complexating effect Effects 0.000 title claims description 12
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 8
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- 239000001263 FEMA 3042 Substances 0.000 claims description 10
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 10
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- 235000005487 catechin Nutrition 0.000 claims description 4
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- 235000004515 gallic acid Nutrition 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
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- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 claims description 2
- YXOLAZRVSSWPPT-UHFFFAOYSA-N Morin Chemical compound OC1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 YXOLAZRVSSWPPT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 claims description 2
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- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 claims description 2
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 claims description 2
- 235000005493 rutin Nutrition 0.000 claims description 2
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 claims description 2
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 claims description 2
- 229960004555 rutoside Drugs 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
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- 239000002131 composite material Substances 0.000 description 12
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 7
- AWZSCLSESMYTKN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol methanamine Chemical compound CN.C(O)C(CC)(CO)CO AWZSCLSESMYTKN-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/238—Tannins, e.g. gallotannic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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Abstract
本发明提供了一种碳纤维表面通过络合作用改性的方法，属于表面改性方法技术领域。所述方法包括：将碳纤维浸入pH为7‑10的含有多酚的缓冲溶液中，常温处理12‑48h后洗涤得到产物1，同时将氧化石墨烯加入pH为7‑10的含有多酚的缓冲溶液中，常温处理12‑48h后取上清液，得到溶液2，将产物1浸没在过渡金属离子溶液30‑60min再浸没在溶液2中30‑60min得到最终产物。本发明采用的原料绿色环保，且反应条件温和，工艺简单，时效短，应用本发明方法制得的改性后的碳纤维表面润湿性和结合性好，与树脂基体的界面强度高。
The invention provides a method for modifying the surface of carbon fibers by complexation, belonging to the technical field of surface modification methods. The method includes: immersing the carbon fiber in a buffer solution containing polyphenols with a pH of 7-10, washing at room temperature for 12-48 hours to obtain a product 1, and adding graphene oxide to the buffer solution containing polyphenols with a pH of 7-10 at the same time. In the solution, after 12-48h treatment at room temperature, the supernatant is taken to obtain solution 2, and product 1 is immersed in the transition metal ion solution for 30-60min and then immersed in solution 2 for 30-60min to obtain the final product. The raw materials used in the present invention are green and environmentally friendly, and the reaction conditions are mild, the process is simple, and the aging time is short.
Description
Technical Field
The invention belongs to the technical field of carbon fiber materials, and particularly relates to a carbon fiber surface complexing modification method.
Background
Carbon Fiber (CF) is a novel fiber material of high-strength and high-modulus fiber with the carbon content of more than 95%, and has a plurality of excellent properties, the carbon fiber has high axial strength and modulus, low density, high specific performance, no creep, ultrahigh temperature resistance under non-oxidation environment, good fatigue resistance, specific heat and conductivity between nonmetal and metal, small thermal expansion coefficient, anisotropy, good corrosion resistance and the like, so the carbon fiber is suitable for being used as a reinforcing material to be compounded with resin, metal, ceramic, carbon and the like to manufacture advanced composite materials. However, the carbon fiber has large surface inertness, low surface energy, lack of chemically active functional groups, low reactivity, poor adhesion with a matrix and more defects in an interface, directly influences the mechanical property of the composite material and limits the exertion of the high performance of the carbon fiber. Therefore, it is necessary to modify the surface of the carbon fiber to improve the wettability and adhesion of the carbon fiber to the matrix, improve the interfacial properties, and further improve the mechanical properties of the composite material.
In view of the many defects on the surface of carbon fiber, various methods for modifying the surface of carbon fiber have been proposed by those skilled in the art, but these methods still have certain disadvantages. For example, plasma treatment has high requirements on devices, concentration factors and the like are difficult to control in the treatment process, and the plasma treatment is only suitable for laboratory research; the oxidation time of liquid-phase oxidation treatment is difficult to control, and mechanical properties of carbon fibers are reduced due to too long time; the consumption of electric energy by electrochemical treatment is very large, and the electrolyte is difficult to treat and pollutes the environment; the irradiation treatment has high requirements on equipment and high energy consumption, and does not accord with the green chemical concept.
Disclosure of Invention
The invention aims to provide a method for complexing and modifying the surface of carbon fiber, which can increase active groups, improve the surface polarity and enhance the interface performance of a carbon fiber resin composite material on the premise of not damaging the strength of the carbon fiber.
The technical scheme of the invention is as follows:
a carbon fiber surface complexing modification method preferably comprises the following steps:
soaking carbon fiber in buffer solution with pH value of 7-10 and dissolved with polyphenol, stirring at normal temperature for 12-48h, and repeatedly washing with deionized water for 2-10min to obtain product 1;
adding graphene oxide into a buffer solution with pH value of 7-10 and dissolved with polyphenol, stirring at normal temperature for 12-48h, and taking supernatant to obtain a solution 2;
and immersing the product 1 in a solution containing transition metal ions for 30-60min, then immersing the product in the solution 2 for 30-60min, and washing and drying to obtain the modified carbon fiber.
Preferably, the carbon fibers are large tow carbon fibers or small tow carbon fibers.
Preferably, the carbon fiber is one of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber or graphite carbon fiber.
Preferably, the polyphenol is a molecule containing a catechol or pyrogallol structure.
Preferably, the polyphenol is one or more of catechol, pyrogallol, gallic acid, tannic acid, catechin, morin or rutin which are mixed in any proportion.
Preferably, the mass ratio of the carbon fibers to the graphene oxide is 1: 0.5-1.
Preferably, the buffer is a tris aqueous solution, and the concentration of the polyphenol in the buffer is 0.5mg/mL-10 mg/mL.
Preferably, the pH of the buffer in which the polyphenol is dissolved is 8.5.
Preferably, the transition metal ion is one of ferric ion, cobalt ion or nickel ion, and the concentration of the transition metal ion is 10mg/mL-50 mg/mL.
Preferably, the specific operation flow of washing and drying includes: washing the mixture to be neutral by using deionized water, and then drying the mixture in vacuum for 12 to 24 hours at the temperature of between 40 and 80 ℃.
The invention has the beneficial effects that:
1. the raw material o-phenyl polyphenol used in the invention has good adhesion capability in a plurality of matrixes, a stable five-membered ring complex is quickly formed by the complexation of the carbon fiber and the o-phenyl polyphenol coated on the surface of the graphene oxide and transition metal ions, the graphene oxide is grafted to the surface of the carbon fiber to modify the surface of the inert carbon fiber, and a large number of oxygen-containing groups can be introduced to the surface of the carbon fiber to improve the wettability and the associativity of resin and the surface of the carbon fiber, so that the interface strength between the carbon fiber and the resin matrix is improved, and the introduction of the graphene oxide also enhances the conductivity of the modified carbon fiber;
2. the method has the advantages of simple treatment process, short reaction time, environmental friendliness, no need of harsh conditions such as strong acid, strong alkali, high temperature and the like, and no damage to the strength of the fiber body.
Drawings
FIG. 1 is a scanning electron micrograph of untreated carbon fibers;
FIG. 2 is a scanning electron micrograph of a modified carbon fiber prepared according to example 1;
FIG. 3 is a Fourier infrared spectrum of untreated carbon fiber, product 1 of example 1, and modified carbon fiber, wherein a, b, c represent untreated carbon fiber, product 1, and modified carbon fiber, respectively;
FIG. 4 is an X-ray photoelectron spectrum of untreated carbon fibers;
FIG. 5 is an X-ray photoelectron spectrum of the modified carbon fiber prepared in example 1;
FIG. 6 is a Ni2p peak plot of an X-ray photoelectron spectrum of the modified carbon fiber prepared in example 1;
FIG. 7 is a narrow spectrum of Ni2p characteristic peaks of an X-ray photoelectron spectrum of the modified carbon fiber prepared in example 1;
fig. 8 is a graph comparing the shear strength of the modified carbon fiber composite prepared in example 1 with that of an untreated carbon fiber composite, wherein a and b represent the untreated carbon fiber composite and the modified carbon fiber composite, respectively.
Detailed Description
The following specific examples are further illustrative of the technical solutions of the present invention, but should not be construed as limiting the invention, and the raw materials in the practice process are all commercially available.
Example 1:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trimethylolpropane aminomethane water solution with pH of 8.5 and 2.5g of tannic acid dissolved in the solution, the solution is stirred for 12 hours at normal temperature, and then the solution is repeatedly washed for 2 minutes by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of trihydroxymethyl aminomethane buffer aqueous solution with pH of 8.5 and dissolved with 2.5g of tannic acid, stirring at normal temperature for 12h, and taking supernatant to obtain solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Scanning electron microscope analysis is respectively carried out on the untreated carbon fiber and the modified carbon fiber, wherein fig. 1 is a scanning electron microscope picture of the untreated carbon fiber, fig. 2 is a scanning electron microscope picture of the modified carbon fiber, and a comparison shows that the surface of the modified carbon fiber is grafted with a uniform graphene oxide coating.
Fourier infrared spectrum analysis is respectively carried out on the untreated carbon fiber, the product 1 and the modified carbon fiber, the results respectively correspond to curves a, b and c in figure 3, and it can be seen that the untreated carbon fiber and the product 1 are all in the range of 3420cm-1A strong stretching vibration peak appears, which corresponds to-OH, 1203cm in the spectrogram of the product 1-1、761cm-1The positions respectively correspond to the stretching vibration of-OH in catechol/pyrogallol in tannic acid and the characteristic peak of TA, and 1726cm in a spectrogram of the modified carbon fiber-1、1226cm-1And 1100cm-1Respectively correspond to graphene oxideC ═ O stretching vibration peak, epoxy stretching vibration peak, and alkoxy stretching vibration peak on (d).
The X-ray photoelectron spectroscopy analysis is respectively carried out on the untreated carbon fiber and the modified carbon fiber to respectively obtain spectrograms shown in fig. 4 and fig. 5, and the comparison shows that in the spectrogram of the modified carbon fiber, a characteristic peak added with Ni2p can be observed at the position of 870eV of binding energy, and the characteristic peak of corresponding elements is changed due to the fact that the graphene oxide layer is deposited on the surface of the carbon fiber, and the C1s peak at the position of 290eV is relatively enhanced.
The peak separation of Ni2p to obtain FIG. 6 shows that the Ni2p peak is composed of Ni-O group with binding energy of about 861eV, which is derived from polyphenol-metal ion complex layer on the surface of carbon fiber, and Ni-OH group with binding energy of about 856eV, which is derived from polyphenol-metal ion complex layer on the surface of carbon fiber2+Hydrogen bonding by coordinated water molecules. Fig. 7 is a characteristic peak narrow spectrum of Ni2p, and it can be seen that a main peak appears at a binding energy of 855eV, which is consistent with that of a normal nickel ion spectrum. The above characterization results all confirm that the complex has been successfully deposited on the carbon fiber surface.
Uniformly mixing epoxy resin and 3, 3' -diethyl-4, 4-diaminodiphenylmethane in a mass ratio of 10:3, degassing, placing a unidirectional fiber fabric made of the modified carbon fiber prepared in the embodiment on a mold, covering a flow guide net, sealing the mold by using a vacuum bag, sucking resin glue into the fiber fabric by using a vacuum pump, and then curing the mold at 90 ℃ for 2h, 120 ℃ for 2h and 150 ℃ for 3h by using vacuum to obtain the carbon fiber epoxy resin composite material.
The prepared composite material is subjected to an interlaminar shear strength test to obtain a shear strength columnar comparison graph shown in figure 8, a and b respectively represent the untreated carbon fiber epoxy resin composite material and the modified carbon fiber epoxy resin composite material, the interlaminar shear strength value of the untreated carbon fiber epoxy resin composite material is only 46.21MPa, but the interlaminar shear strength value of the modified carbon fiber composite material is increased to 57.37MPa and is increased by 24.15%.
Example 2:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trimethylolpropane aminomethane water solution with pH of 8.5 and 2.5g of tannic acid dissolved in the solution, the solution is stirred for 12 hours at normal temperature, and then the solution is repeatedly washed for 2 minutes by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of trimethylolpropane aminomethane buffer aqueous solution with pH of 8.5 and dissolved with 2.5g of catechol, stirring at normal temperature for 12h, and taking supernatant to obtain solution 2;
and immersing the product 1 in 500ml of ferric ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Example 3:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trihydroxymethyl aminomethane water solution with pH of 7.5 and 2.5g of tannic acid dissolved in the water solution, stirred for 12 hours at normal temperature, and repeatedly washed for 2 minutes by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of 7.5 pH trihydroxymethyl aminomethane buffer aqueous solution dissolved with 2.5g of catechol, stirring at normal temperature for 12h, and taking supernatant to obtain solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Example 4:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trihydroxymethyl aminomethane water solution with pH of 9.5 and dissolved with 2.5g of tannic acid, stirred for 12 hours at normal temperature, and repeatedly washed for 2 minutes by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of a trimethylolpropane aminomethane buffer aqueous solution with pH of 9.5 and dissolved with 2.5g of catechol, stirring at normal temperature for 12h, and taking supernatant to obtain a solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Example 5:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trimethylolpropane buffer aqueous solution with pH of 8.5 and dissolved with 2.5g of catechin, stirred for 12 hours at normal temperature, and repeatedly washed for 2 minutes by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of trimethylolpropane water solution with pH of 8.5 and dissolved with 2.5g of catechin, stirring at normal temperature for 12 hours, and taking supernatant to obtain solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Example 6:
0.625g of small tow polyacrylonitrile-based carbon fiber is immersed in 500ml of trihydroxymethyl aminomethane buffer aqueous solution with pH of 8.5 and dissolved with 2.5g of gallic acid, stirred for 12h at normal temperature, and repeatedly washed for 2min by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of trimethylolpropane aminomethane aqueous solution with pH of 8.5 and dissolved with 2.5g of gallic acid, stirring at normal temperature for 12h, and taking supernatant to obtain solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Example 7:
0.625g of macrotow polyacrylonitrile-based carbon fiber is immersed in 500ml of trihydroxymethyl aminomethane buffer aqueous solution with pH of 8.5 and dissolved with 2.5g of tannic acid, stirred for 12h at normal temperature, and repeatedly washed for 2min by deionized water to obtain a product 1;
adding 0.625g of graphene oxide into 500ml of a trihydroxymethyl aminomethane aqueous solution with pH of 8.5 and 2.5g of tannic acid dissolved in the aqueous solution, stirring the mixture at normal temperature for 12 hours, and taking supernatant to obtain a solution 2;
and immersing the product 1 in 500ml of nickel ion solution for 40min, immersing in the solution 2 for 45min, washing to be neutral by deionized water, and then drying in vacuum at 50 ℃ for 24h to obtain the modified carbon fiber.
Claims (10)
1. A carbon fiber surface complexing modification method is characterized by comprising the following steps:
soaking carbon fiber in buffer solution with pH value of 7-10 and dissolved with polyphenol, stirring at normal temperature for 12-48h, and repeatedly washing with deionized water for 2-10min to obtain product 1;
adding graphene oxide into a buffer solution with pH value of 7-10 and dissolved with polyphenol, stirring at normal temperature for 12-48h, and taking supernatant to obtain a solution 2;
and immersing the product 1 in a solution containing transition metal ions for 30-60min, then immersing the product in the solution 2 for 30-60min, and washing and drying to obtain the modified carbon fiber.
2. The carbon fiber surface complexation modification method according to claim 1, wherein the carbon fiber is a large-tow carbon fiber or a small-tow carbon fiber.
3. The carbon fiber surface complexation modification method according to claim 1, wherein the carbon fiber is one of a polyacrylonitrile-based carbon fiber, a pitch-based carbon fiber, or a graphite carbon fiber.
4. The carbon fiber surface complexation modification method according to claim 1, wherein the polyphenol is a molecule containing a catechol or pyrogallol structure.
5. The method for complexing and modifying the surface of carbon fibers according to claim 1 or 3, wherein the polyphenol is one or more of catechol, pyrogallol, gallic acid, tannic acid, catechin, morin and rutin, and is mixed in an arbitrary ratio.
6. The carbon fiber surface complexing modification method according to claim 1, wherein the mass ratio of the carbon fibers to the graphene oxide is 1: 0.5-1.
7. The carbon fiber surface complexing modification method according to claim 1, wherein the buffer solution is a tris aqueous solution, and the concentration of the polyphenol in the buffer solution is 0.5mg/mL to 10 mg/mL.
8. The method for complexing and modifying the surface of carbon fiber according to claim 1, wherein the pH of the buffer containing dissolved polyphenol is 8.5.
9. The carbon fiber surface complexing modification method according to claim 1, wherein the transition metal ion is one of ferric ion, cobalt ion or nickel ion, and the concentration of the transition metal ion is 10mg/mL-50 mg/mL.
10. The carbon fiber surface complexing modification method according to claim 1, wherein the specific operation procedures of washing and drying comprise: washing the mixture to be neutral by using deionized water, and then drying the mixture in vacuum for 12 to 24 hours at the temperature of between 40 and 80 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114232135A (en) * | 2022-01-28 | 2022-03-25 | 郑州中远氨纶工程技术有限公司 | Washing-resistant alginate fiber and preparation method thereof |
| CN114990761A (en) * | 2022-06-07 | 2022-09-02 | 东华大学 | A kind of preparation method of antibacterial colored denim fabric containing Porel fiber |
| CN115948909A (en) * | 2022-11-10 | 2023-04-11 | 北京大学 | Preparation method of super-hydrophilic carbon fiber |
| CN116446181A (en) * | 2023-04-18 | 2023-07-18 | 北京化工大学 | A kind of carbon fiber porous layer composite material and its preparation method and application |
| CN116479651A (en) * | 2023-04-04 | 2023-07-25 | 同济大学 | Method for modifying fiber surface |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862428A (en) * | 2016-05-05 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of graphene-modified carbon fiber sizing agent |
| CN107385921A (en) * | 2017-07-12 | 2017-11-24 | 中国航发北京航空材料研究院 | A kind of polyfunctional epoxy resin base water solubility sizing agent containing graphene oxide and preparation method thereof |
| CN108951140A (en) * | 2017-05-18 | 2018-12-07 | 北京化工大学 | A kind of surface modification method of fiber |
| CN110791963A (en) * | 2019-11-20 | 2020-02-14 | 长春工业大学 | A kind of method of carbon fiber surface polymerization modification |
-
2021
- 2021-11-09 CN CN202111319981.2A patent/CN113863001A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862428A (en) * | 2016-05-05 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of graphene-modified carbon fiber sizing agent |
| CN108951140A (en) * | 2017-05-18 | 2018-12-07 | 北京化工大学 | A kind of surface modification method of fiber |
| CN107385921A (en) * | 2017-07-12 | 2017-11-24 | 中国航发北京航空材料研究院 | A kind of polyfunctional epoxy resin base water solubility sizing agent containing graphene oxide and preparation method thereof |
| CN110791963A (en) * | 2019-11-20 | 2020-02-14 | 长春工业大学 | A kind of method of carbon fiber surface polymerization modification |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114232135A (en) * | 2022-01-28 | 2022-03-25 | 郑州中远氨纶工程技术有限公司 | Washing-resistant alginate fiber and preparation method thereof |
| CN114232135B (en) * | 2022-01-28 | 2024-01-26 | 郑州中远氨纶工程技术有限公司 | Washing-resistant alginate fiber and preparation method thereof |
| CN114990761A (en) * | 2022-06-07 | 2022-09-02 | 东华大学 | A kind of preparation method of antibacterial colored denim fabric containing Porel fiber |
| CN114990761B (en) * | 2022-06-07 | 2023-10-20 | 东华大学 | Preparation method of antibacterial colored jean fabric containing Portel fibers |
| CN115948909A (en) * | 2022-11-10 | 2023-04-11 | 北京大学 | Preparation method of super-hydrophilic carbon fiber |
| CN116479651A (en) * | 2023-04-04 | 2023-07-25 | 同济大学 | Method for modifying fiber surface |
| CN116446181A (en) * | 2023-04-18 | 2023-07-18 | 北京化工大学 | A kind of carbon fiber porous layer composite material and its preparation method and application |
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