CN110230129B - Fe-containing material with carbon nano-tube growing on inner and outer surfaces3C hollow composite carbon fiber and preparation method thereof - Google Patents

Fe-containing material with carbon nano-tube growing on inner and outer surfaces3C hollow composite carbon fiber and preparation method thereof Download PDF

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CN110230129B
CN110230129B CN201910515624.XA CN201910515624A CN110230129B CN 110230129 B CN110230129 B CN 110230129B CN 201910515624 A CN201910515624 A CN 201910515624A CN 110230129 B CN110230129 B CN 110230129B
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CN110230129A (en
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姜再兴
韦华伟
黄玉东
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Harbin Institute of Technology
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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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    • 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
    • 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

Fe-containing material with carbon nano-tube growing on inner and outer surfaces3C hollow composite carbon fiber and a preparation method thereof, which relate to a hollow fiber shielding material and a preparation method thereof. The technical problem that the existing carbon fiber and carbon nanotube composite material is poor in electromagnetic shielding effectiveness is solved. The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3The structure of the hollow composite carbon fiber of C is to contain magnetic Fe3The carbon fiber hollow tube of the C nano particles is a carrier, and carbon nano tubes grow on the inner surface and the outer surface of the hollow tube. The preparation method comprises the following steps: firstly, preparing Fe3O4-PAN/PMMA hollow fibers; II, in Fe3O4-growing carbon nanotubes on the inner and outer surfaces of the PAN hollow fiber. The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3The electromagnetic shielding effectiveness of the hollow composite carbon fiber C can reach 80dB, and the hollow composite carbon fiber C can be used in the field of electromagnetic shielding.

Description

Fe-containing material with carbon nano-tube growing on inner and outer surfaces3C hollow composite carbon fiber and preparation method thereof
Technical Field
The invention relates to a hollow fiber shielding material and a preparation method thereof.
Background
At present, electromagnetic pollution becomes the fifth major pollution source following atmospheric pollution, water pollution, noise pollution and soil pollution, and has a tendency of harming physical and psychological health. Unlike other pollutants, atmospheric, water, noise and soil pollution are visible, addressable and directly observable, people can fully recognize the harm of the pollution, but electromagnetic radiation is unscented and addressable, is energy pollution and is relatively hidden in environment pollution. In daily life, when the electromagnetic radiation intensity exceeds the safety and sanitation standard limit value, negative effects are generated on human bodies, and symptoms such as headache, insomnia and the like appear. The harm of electromagnetic radiation has become the focus of health organization in various countries, so the development of shielding and wave-absorbing materials has important significance for preventing the harm of electromagnetic pollution to people.
Carbon-based materials are a common shielding material, and mainly comprise carbon fibers, silicon carbide, conductive graphite, carbon nanotubes, mesoporous carbon and the like. The carbon-containing fiber achieves the purpose of attenuating electromagnetic waves mainly due to eddy current loss generated by skin effect; meanwhile, after the electromagnetic wave is incident, partial phase cancellation phenomenon can occur, and the electromagnetic wave can be attenuated. However, the electromagnetic shielding effectiveness of pure carbon-based materials is generally low, and the electromagnetic shielding effect of the pure carbon-based materials can be improved by modifying the carbon-based materials at present, for example, the surface of carbon fibers is coated with metal, plated with SiC or deposited with graphite carbon particles, and the electromagnetic shielding effectiveness of the obtained composite material is generally 30-40 dB; the electromagnetic shielding effectiveness is about 40-50 dB after the Carbon Nanotube (CNT) is compounded with the organic polymer. The electromagnetic shielding effectiveness is still low.
Disclosure of Invention
The invention aims to solve the technical problem of poor electromagnetic shielding effectiveness of the existing carbon fiber and carbon nanotube composite material, and provides Fe-containing carbon nanotube growing on the inner and outer surfaces3C hollow composite carbon fiber and a preparation method thereof.
The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3C hollow composite carbon fiber, its structure is to contain magnetic Fe3The carbon fiber hollow tube of the C nano particles is a carrier, and carbon nano tubes grow on the inner surface and the outer surface of the hollow tube.
Fe-containing carbon nanotubes grown on the inner and outer surfaces3The preparation method of the hollow composite carbon fiber comprises the following steps:
firstly, preparing Fe3O4PAN/PMMA hollow fibers:
a. mixing Fe3O4Dispersing the nano particles in dimethyl sulfoxide to obtain Fe3O4A nanoparticle dispersion liquid; adding polyacrylonitrile into DMSO, heating and dissolving to obtain a polyacrylonitrile solution; mixing Fe3O4Mixing the nano particle dispersion liquid with a polyacrylonitrile solution to obtain a mixed liquid; evaporating part of the solvent under reduced pressure to obtain a shell solution;
b. preparing a DMSO (dimethyl sulfoxide) solution of polymethyl methacrylate (PMMA) to obtain a core layer solution;
c. taking a DMSO (dimethyl sulfoxide) aqueous solution as a coagulating bath, introducing a core layer solution into a central cavity of a double-channel coaxial spinneret of a spinning machine, introducing a shell layer solution into an annular cavity of the double-channel coaxial spinneret of the spinning machine, and spinning by using a dry-jet wet spinning technology;
d. immersing the spun fiber in methanol at the temperature of-30 to-20 ℃ to remove the solvent in the fiber to obtain Fe3O4-PAN/PMMA sheath-core fibers;
e. mixing Fe3O4-immersing the PAN/PMMA sheath-core fiber in acetone with intermittent ultrasonic treatment to remove PMMA from the fiber and obtain Fe3O4-PAN hollow fibers;
II, in Fe3O4-growing carbon nanotubes on the inner and outer surfaces of the PAN hollow fiber:
f. mixing Fe3O4-immersing PAN hollow fibres in a toluene solution of ferrocene, with intermittent sonication,
g. f, treating the Fe treated in the step f3O4-after drying the PAN hollow fibres, placing them in a CVD tube furnace and applying tension at both ends of the fibres;
h. heating a CVD tube furnace to 200-300 ℃ and keeping for 1-2 h to carry out pre-oxidation treatment on the fibers; then introducing argon for 1-1.2 h, then continuously heating to 600-620 ℃, and introducing hydrogen for reaction for 30-60 min while keeping the temperature; then continuously heating to 800-820 ℃, introducing a toluene solution of ferrocene by taking argon/hydrogen mixed gas as a carrier at the temperature, reacting for 1-4 h, growing carbon nano tubes on the inner and outer surfaces of the hollow fiber in the process, and simultaneously, Fe3O4Conversion of precursor to Fe3C, cooling to room temperature to obtain Fe-containing carbon nano tubes growing on the inner and outer surfaces3C, hollow composite fibers.
The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3C, firstly preparing nano magnetic Fe by using a double-channel spinning head3O4-Polyacrylonitrile (PAN)/Polymethylmethacrylate (PMMA) sheath-core structured fibers,dissolving PMMA to obtain doped Fe3O4Hollow PAN fiber of the precursor, then growing carbon nano-tubes on the inner and outer surfaces of the hollow fiber, and preparing the magnetic Fe containing carbon nano-tubes grown on the inner and outer surfaces3C, hollow carbon fiber material of nano particles. Hollow Fe3Carbon Nanotubes (CNTs) grow on the inner and outer surfaces of the C-carbon fibers, and electromagnetic waves are subjected to dielectric loss when passing through the carbon nanotubes, so that the loss is easy to occur at the joints of the fibers and the CNTs, and the intensity of the electromagnetic waves is attenuated; magnetic Fe3The C nano particles adjust the magnetic property of the material, so that the whole material achieves the matching of dielectric loss and magnetic loss, and the electromagnetic wave intensity is further attenuated. After high-temperature carbonization, PAN is converted into carbon to form the carbon fiber with a one-dimensional hollow tubular structure, and electromagnetic waves are reflected for multiple times in the hollow cavity to further attenuate the intensity of the electromagnetic waves. Due to the special structures, the material has excellent electromagnetic shielding performance.
The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3C hollow composite carbon fiber, in which high-conductivity CNT is used to reinforce the dielectric loss of material against electromagnetic waves without shedding ferromagnetic Fe3The C particles endow the material with permanent magnetic property and the characteristic of magnetic loss, and the shielding property of the material can reach the best through the synergistic effect of the C particles, the C particles and the material. The invention relates to Fe-containing carbon nano-tube with growing inner and outer surfaces3The electromagnetic shielding effectiveness of the hollow composite carbon fiber C can reach more than 80dB, and the hollow composite carbon fiber C can be used in the field of electromagnetic shielding.
Drawings
FIG. 1 shows Fe obtained in step d of example 13O4-scanning electron micrographs of the PAN/PMMA sheath-core fiber surface;
FIG. 2 shows Fe obtained in step d of example 13O4-scanning electron micrographs of PAN/PMMA sheath-core fiber cross-sections;
FIG. 3 shows Fe obtained in step e of example 13O4-scanning electron micrographs of PAN hollow fibers;
FIG. 4 shows Fe content of the carbon nanotubes grown on the inner and outer surfaces obtained in step h of example 13Scanning electron microscope photograph of outer surface of hollow composite carbon fiber of CSlicing;
FIG. 5 shows Fe-containing carbon nanotubes grown on the inner and outer surfaces obtained in step h of example 13A scanning electron microscope photograph of the inner surface of the hollow composite carbon fiber of C;
FIG. 6 shows Fe content of carbon nanotubes grown on the inner and outer surfaces obtained in step h of example 13An XRD (X-ray diffraction) curve diagram of the hollow composite carbon fiber of C;
FIG. 7 is the Fe-containing carbon nanotubes grown on the inner and outer surfaces obtained in step h of example 13And C, electromagnetic shielding effectiveness curve of the hollow composite carbon fiber.
Detailed Description
The first embodiment is as follows: fe-containing carbon nanotubes grown on the inner and outer surfaces according to the present embodiment3C hollow composite carbon fiber, its structure is to contain magnetic Fe3The carbon fiber hollow tube of the C nano particles is a carrier, and carbon nano tubes grow on the inner surface and the outer surface of the hollow tube.
The second embodiment is as follows: fe-containing carbon nanotubes grown on the inner and outer surfaces according to the present embodiment3The preparation method of the hollow composite carbon fiber comprises the following steps:
firstly, preparing Fe3O4PAN/PMMA hollow fibers:
a. mixing Fe3O4Dispersing the nano particles in dimethyl sulfoxide to obtain Fe3O4A nanoparticle dispersion liquid; adding polyacrylonitrile into DMSO, heating and dissolving to obtain a polyacrylonitrile solution; mixing Fe3O4Mixing the nano particle dispersion liquid with a polyacrylonitrile solution to obtain a mixed liquid; evaporating part of the solvent under reduced pressure to obtain a shell solution;
b. preparing a DMSO (dimethyl sulfoxide) solution of polymethyl methacrylate (PMMA) to obtain a core layer solution;
c. taking a DMSO (dimethyl sulfoxide) aqueous solution as a coagulating bath, introducing a core layer solution into a central cavity of a double-channel coaxial spinneret of a spinning machine, introducing a shell layer solution into an annular cavity of the double-channel coaxial spinneret of the spinning machine, and spinning by using a dry-jet wet spinning technology;
d. the spun fiber is immersed in the solution at the temperature of-30 to-2Soaking in methanol at 0 deg.C to remove solvent from fiber to obtain Fe3O4-PAN/PMMA sheath-core fibers;
e. mixing Fe3O4-immersing the PAN/PMMA sheath-core fiber in acetone with intermittent ultrasonic treatment to remove PMMA from the fiber and obtain Fe3O4-PAN hollow fibers;
II, in Fe3O4-growing carbon nanotubes on the inner and outer surfaces of the PAN hollow fiber:
f. mixing Fe3O4-immersing PAN hollow fibres in a toluene solution of ferrocene, with intermittent sonication,
g. f, treating the Fe treated in the step f3O4-after drying the PAN hollow fibres, placing them in a CVD tube furnace and applying tension at both ends of the fibres;
h. heating a CVD tube furnace to 200-300 ℃ and keeping for 1-2 h to carry out pre-oxidation treatment on the fibers; then introducing argon for 1-1.2 h, then continuously heating to 600-620 ℃, and introducing hydrogen for reaction for 30-60 min while keeping the temperature; then continuously heating to 800-820 ℃, introducing a toluene solution of ferrocene by taking argon/hydrogen mixed gas as a carrier at the temperature, reacting for 1-4 h, growing carbon nano tubes on the inner and outer surfaces of the hollow fiber in the process, and simultaneously, Fe3O4Conversion of precursor to Fe3C, cooling to room temperature to obtain Fe-containing carbon nano tubes growing on the inner and outer surfaces3C, hollow composite fibers.
The third concrete implementation mode: the second difference between the present embodiment and the present embodiment is that the magnetic Fe in the first step3O4The preparation method of the nano particles comprises the following steps: 1.35-2.7 g FeCl3·6H2O, 3.6-7.2 g of anhydrous sodium acetate, 0-1 g of polyethylene glycol and 80ml of ethylene glycol are mixed, ultrasonically and fully stirred uniformly, put into a polytetrafluoroethylene reaction kettle, reacted at 190-210 ℃ for 8-10 h, then cleaned by ethanol, and dried in a vacuum oven to obtain magnetic Fe3O4Nanoparticles. The rest is the same as the second embodiment.
The fourth concrete implementation mode: this embodiment and specific implementationThe second or third difference is that in the first step, Fe is contained in the mixed solution3O4The mass of the nano particles is Fe3O45 to 30 percent of the total mass of the nano particles and the polyacrylonitrile. The other is the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that in the first step a, the concentration of polyacrylonitrile after partial solvent is evaporated under reduced pressure reaches 250-350 g/L. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and the second to the fifth embodiment is that in the first step b, the concentration of the polymethyl methacrylate in the core layer solution is 500-700 g/L. The other is the same as one of the second to fifth embodiments.
The seventh embodiment: the present embodiment is different from the second to sixth embodiments in that in the first step c, the DMSO aqueous solution as the coagulation bath has a mass percentage concentration of 40% to 50%. The other is the same as one of the second to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and the second to seventh embodiments is that in the first step, the soaking time of the fiber yarn in methanol is 3 to 5 days. The rest is the same as one of the second to seventh embodiments.
The specific implementation method nine: this embodiment differs from the second to eighth embodiment in that in step one e, Fe3O4The soaking time of the PAN/PMMA sheath-core fiber in acetone is 3-4 days. The rest is the same as the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment is different from the second to ninth embodiments in that in the first step e, the intermittent ultrasonic treatment is ultrasonic treatment for 10 to 15 minutes every 2 to 4 hours. The other is the same as in one of the second to ninth embodiments.
The concrete implementation mode eleven: this embodiment differs from the second to tenth embodiments in that in step two f, Fe3O4And soaking the PAN hollow fiber in a toluene solution of ferrocene for 2-3 days. OthersThe same as in one of the second to tenth embodiments.
The specific implementation mode twelve: the difference between the second embodiment and the first embodiment is that in the second step, the mass percentage concentration of the ferrocene in the toluene solution of the ferrocene is 5-10 wt%. The other is the same as in one of the second to eleventh embodiments.
The specific implementation mode is thirteen: the present embodiment is different from the second to twelfth embodiments in that in the second step f, the intermittent ultrasonic treatment is ultrasonic treatment for 10 to 15 minutes every 2 to 4 hours. The rest is the same as the second to twelfth embodiments.
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: fe-containing carbon nanotubes grown on the inner and outer surfaces of this example3The preparation method of the hollow composite carbon fiber comprises the following steps:
firstly, preparing Fe3O4PAN/PMMA hollow fibers:
a. mixing 3gFe3O4The nano particles are ultrasonically dispersed in 100ml of dimethyl sulfoxide to obtain Fe3O4A nanoparticle dispersion liquid; adding 27g of polyacrylonitrile with the molecular weight of 48000-50000 into 100ml of DMSO, and heating to 110 ℃ to dissolve the polyacrylonitrile to obtain a polyacrylonitrile solution; mixing Fe3O4The nano particle dispersion liquid is mixed with the polyacrylonitrile solution, then Fe3O4The mass of the nano particles is Fe3O4The total mass of the nano particles and the polyacrylonitrile is 10 percent, and the solvent is evaporated under reduced pressure to ensure that the concentration of the polyacrylonitrile reaches 30g/100ml, thus obtaining a shell solution;
b. adding 60g of polymethyl methacrylate (PMMA) into 100ml of DMSO, and dissolving to obtain a core layer solution; wherein the concentration of the polymethyl methacrylate is 60g/100 ml;
c. taking a DMSO (dimethyl sulfoxide) aqueous solution with the mass percentage concentration of 50% as a coagulating bath, introducing a core layer solution into a central cavity of a double-channel coaxial spinneret of a spinning machine, introducing a shell layer solution into an annular cavity of the double-channel coaxial spinneret of the spinning machine, and spinning by using a dry-jet wet spinning technology; the volume flow ratio of the shell layer solution to the core layer solution is 1: 1;
d. soaking the spun fiber in low temperature methanol at-20 deg.C for 3 days to remove solvent in the fiber to obtain Fe3O4-PAN/PMMA sheath-core fibers;
e. mixing Fe3O4-the PAN/PMMA sheath-core fiber is immersed in acetone for 3 days with intermittent ultrasound every 4 hours for 10 minutes to remove PMMA from the fiber and obtain Fe3O4-PAN hollow fibers;
II, in Fe3O4-growing carbon nanotubes on the inner and outer surfaces of the PAN hollow fiber:
f. mixing Fe3O4Soaking the PAN hollow fiber in a ferrocene toluene solution for 2 days, intermittently performing ultrasonic treatment for 10 minutes every 4 hours, wherein the mass percentage concentration of ferrocene in the ferrocene toluene solution is 10%;
g. f, treating the Fe treated in the step f3O4After drying the PAN hollow fiber, putting the PAN hollow fiber into a CVD tube furnace, and applying tension to two ends of the PAN hollow fiber;
h. heating a CVD tube furnace to 240 ℃ and keeping the temperature for 1h, keeping the temperature at 285 ℃ for 30min, and carrying out pre-oxidation treatment on the fibers; then argon is introduced for 1h, then the temperature is continuously raised to 600 ℃, and hydrogen is introduced for reaction for 30min while the temperature is kept; then continuously heating to 800 ℃, introducing a toluene solution of ferrocene by taking argon/hydrogen mixed gas as a carrier at the temperature, reacting for 4 hours, and growing carbon nano tubes on the inner and outer surfaces of the hollow carbonized fiber and simultaneously Fe3O4Conversion of precursor to Fe3C, cooling to room temperature to obtain Fe-containing carbon nano tubes growing on the inner and outer surfaces3C, hollow composite carbon fiber.
Wherein in the first step, magnetic Fe3O4The preparation method of the nano particles comprises the following steps:
2.7g FeCl3·6H2O, 7.2g of anhydrous sodium acetate, 1.0g of polyethylene glycol and 80ml of ethylene glycol are mixed, fully stirred by ultrasonic for 30 minutes to be uniform, then put into a polytetrafluoroethylene reaction kettle, reacted for 8 hours at 200 ℃, then washed with ethanol for three times, and finally put into a vacuum oven at medium temperatureDrying at 60 deg.C for 12 hr to obtain magnetic Fe3O4Nanoparticles.
In this example, Fe obtained in step d3O4The scanning electron micrograph of the surface of the PAN/PMMA sheath-core fiber is shown in FIG. 1, the scanning electron micrograph of the cross section is shown in FIG. 2, and as can be seen from FIG. 1, the surface of the fiber is smooth, and the spots therein are Fe3O4Are gathered together to form. As can be seen in fig. 2, the fibers have a clear sheath-core structure and the thickness of the sheath fibers is relatively uniform, indicating successful production of sheath-core fibers.
In this example, Fe obtained in step e3O4The scanning electron micrograph of the PAN hollow fiber is shown in fig. 3, and it can be seen from fig. 3 that the PAN hollow fiber has uniform thickness and regular cross-sectional morphology. While the PMMA inside the fiber has been completely removed.
In this example, the Fe-containing carbon nanotubes grown on the inner and outer surfaces obtained in step h3A scanning electron micrograph of the outer surface of the hollow composite carbon fiber of C is shown in fig. 4, and it can be seen from fig. 4 that the CNT completely covers the surface of the fiber, forming a thicker CNT shell layer on the outer surface of the hollow fiber. The scanning electron micrograph of the inner surface is shown in fig. 5, and it can be seen from fig. 5 that CNTs also grow on the inner surface of the fiber, indicating that CNTs grow on both the inner and outer surfaces of the hollow fiber.
Growing carbon nanotubes on the inner and outer surfaces of the hollow carbonized fiber in the step h, wherein Fe is contained in the hollow carbonized fiber3O4Conversion of precursor to Fe3C, as shown in FIG. 6, Fe-containing carbon nanotubes grown on the inner and outer surfaces3XRD spectrogram of hollow composite carbon fiber of C and Fe3O4The spectrogram contrast shows that the characteristic peak is obviously changed and Fe appears between 30 and 50 DEG3Characteristic peak of C.
Fe-containing carbon nanotubes grown on the inner and outer surfaces prepared in this example3Cutting the hollow composite carbon fiber C into short fibers of 10mm, mixing the short fibers with paraffin according to the mass percentage of 20%, and manufacturing a test sample with the length multiplied by the width multiplied by the height multiplied by 22.9mm multiplied by 10.2mm multiplied by h mm by a mould, wherein h is 0.5mm and 1mm1.5mm and 2mm, electromagnetic shielding performance tests were performed on test samples of different thicknesses, and the results are shown in fig. 7. As can be seen from fig. 7, the electromagnetic shielding performance of the material with 20% of fibers and a thickness of 2mm can reach 80 dB.
In this embodiment, after the electromagnetic wave is incident on the hollow composite carbon fiber, the hollow Fe is formed3Carbon Nanotubes (CNTs) grow on the inner and outer surfaces of the C-carbon fibers, and electromagnetic waves are subjected to dielectric loss when passing through the carbon nanotubes, so that the loss is easy to occur at the joints of the fibers and the CNTs, and the intensity of the electromagnetic waves is attenuated; magnetic Fe3The C nano particles adjust the magnetic property of the material, so that the material has magnetic loss performance, and the electromagnetic wave intensity is further attenuated. PAN is converted into carbon through high-temperature carbonization, the carbon fiber is in a one-dimensional hollow tubular structure, and electromagnetic waves are reflected for multiple times in the hollow cavity to further attenuate the intensity of the electromagnetic waves. Due to the special structures, the material has excellent electromagnetic shielding performance.
In this example, the carbon nanotubes grown on the inner and outer surfaces contained Fe3Fe in hollow composite carbon fiber of C3C is obtained by adding Fe in the spinning process3O4Precursor, Fe converted to ferromagnetic at high temperature3And C, the method improves the stability of the magnetic particles in the material, prevents the magnetic particles from falling off, and enables the magnetism of the material to be maintained for a long time, thereby enabling the performance to be stable.

Claims (9)

1. Fe-containing material with carbon nano-tube growing on inner and outer surfaces3The preparation method of the hollow composite carbon fiber is characterized by comprising the following steps of:
firstly, preparing Fe3O4PAN/PMMA hollow fibers:
a. mixing Fe3O4Dispersing the nano particles in dimethyl sulfoxide to obtain Fe3O4A nanoparticle dispersion liquid; adding polyacrylonitrile into DMSO, heating and dissolving to obtain a polyacrylonitrile solution; mixing Fe3O4Mixing the nano particle dispersion liquid with a polyacrylonitrile solution to obtain a mixed liquid; evaporating part of the solvent under reduced pressure to obtain a shell solution;
b. preparing a DMSO solution of polymethyl methacrylate to obtain a core layer solution;
c. taking a DMSO (dimethyl sulfoxide) aqueous solution as a coagulating bath, introducing a core layer solution into a central cavity of a double-channel coaxial spinneret of a spinning machine, introducing a shell layer solution into an annular cavity of the double-channel coaxial spinneret of the spinning machine, and spinning by using a dry-jet wet spinning technology;
d. immersing the spun fiber in methanol at the temperature of-30 to-20 ℃ to remove the solvent in the fiber to obtain Fe3O4-PAN/PMMA sheath-core fibers;
e. mixing Fe3O4-immersing the PAN/PMMA sheath-core fiber in acetone with intermittent ultrasonic treatment to remove PMMA from the fiber and obtain Fe3O4-PAN hollow fibers;
II, in Fe3O4-growing carbon nanotubes on the inner and outer surfaces of the PAN hollow fiber:
f. mixing Fe3O4-immersing PAN hollow fibers in a toluene solution of ferrocene, with intermittent sonication;
g. f, treating the Fe treated in the step f3O4-after drying the PAN hollow fibres, placing them in a CVD tube furnace and applying tension at both ends of the fibres;
h. heating a CVD tube furnace to 200-300 ℃ and keeping for 1-2 h to carry out pre-oxidation treatment on the fibers; then introducing argon for 1-1.2 h, then continuously heating to 600-620 ℃, and introducing hydrogen for reaction for 30-60 min while keeping the temperature; then continuously heating to 800-820 ℃, introducing a toluene solution of ferrocene by taking argon/hydrogen mixed gas as a carrier at the temperature, reacting for 1-4 h, growing carbon nano tubes on the inner and outer surfaces of the hollow fiber in the process, and simultaneously, Fe3O4Conversion of precursor to Fe3C, cooling to room temperature to obtain Fe-containing carbon nano tubes growing on the inner and outer surfaces3C, hollow composite fibers; the structure of the fiber is to contain magnetic Fe3The carbon fiber hollow tube of the C nano particles is a carrier, and carbon nano tubes grow on the inner surface and the outer surface of the hollow tube.
2. The method of claim 1Fe-containing material with carbon nano-tube growing on inner and outer surfaces3The preparation method of the hollow composite carbon fiber C is characterized in that the magnetic Fe in the step one3O4The preparation method of the nano particles comprises the following steps: 1.35-2.7 g FeCl3·6H2O, 3.6-7.2 g of anhydrous sodium acetate, 0-1 g of polyethylene glycol and 80ml of ethylene glycol are mixed, ultrasonically stirred uniformly, put into a polytetrafluoroethylene reaction kettle, reacted at 190-210 ℃ for 8-10 h, then cleaned by ethanol, and dried in a vacuum oven to obtain magnetic Fe3O4Nanoparticles.
3. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23The preparation method of the hollow composite carbon fiber C is characterized in that in the step one a, Fe is contained in the mixed solution3O4The mass of the nano particles is Fe3O45 to 30 percent of the total mass of the nano particles and the polyacrylonitrile.
4. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23The preparation method of the hollow composite carbon fiber is characterized in that in the step one a, the concentration of polyacrylonitrile reaches 250-350 g/L after partial solvent is evaporated under reduced pressure.
5. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23The preparation method of the hollow composite carbon fiber is characterized in that in the step one b, the concentration of the polymethyl methacrylate in the core layer solution is 500-700 g/L.
6. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23The preparation method of the hollow composite carbon fiber is characterized in that in the step one C, the mass percentage concentration of the DMSO aqueous solution used as the coagulating bath is 40-50%.
7. The method of claim 1 or 2, wherein the inner and outer surfaces of the carbon nanotubes are grownWith Fe3The preparation method of the hollow composite carbon fiber is characterized in that in the step one e, intermittent ultrasonic treatment refers to ultrasonic treatment for 10-15 minutes every 2-4 hours.
8. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23And C, the preparation method of the hollow composite carbon fiber is characterized in that in the second step f, the mass percentage concentration of the ferrocene in the toluene solution of the ferrocene is 5-10 wt%.
9. Fe-containing material for growing carbon nanotubes on inner and outer surfaces according to claim 1 or 23The preparation method of the hollow composite carbon fiber is characterized in that in the second step f, intermittent ultrasonic treatment refers to ultrasonic treatment for 10-15 minutes every 2-4 hours.
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