CN111235695A - Preparation method of porous carbon fiber electromagnetic wave absorbing agent - Google Patents

Preparation method of porous carbon fiber electromagnetic wave absorbing agent Download PDF

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Publication number
CN111235695A
CN111235695A CN202010189176.1A CN202010189176A CN111235695A CN 111235695 A CN111235695 A CN 111235695A CN 202010189176 A CN202010189176 A CN 202010189176A CN 111235695 A CN111235695 A CN 111235695A
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carbon fiber
porous carbon
electromagnetic wave
product
wave absorber
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CN111235695B (en
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姬广斌
陈家彬
顾未华
张铸
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Jiangsu Yangzi Xinfu Shipbuilding Co Ltd
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Nanjing University of Aeronautics and Astronautics
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/00—Materials not provided for elsewhere
    • 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
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract

The invention discloses a preparation method of a porous carbon fiber electromagnetic wave absorbing agent, which comprises the following steps: (1) sequentially adding PVP, ethyl orthosilicate and iron acetylacetonate into N, N-dimethylformamide, and stirring at high temperature until the PVP, the ethyl orthosilicate and the iron acetylacetonate are completely dissolved; (2) putting the solution prepared in the step (1) into an injector, carrying out electrostatic spinning, collecting a product obtained after spinning, and drying the product in vacuum; placing the dried product in argon gas for calcination treatment; (3) and (3) soaking the calcined product obtained in the step (2) in HF, performing centrifugal separation after soaking, and collecting the separated product. Compared with the traditional wave-absorbing material, the porous carbon fiber material prepared by the method has high absorption strength under low thickness, and the wave-absorbing performance of the material is adjustable due to the adjustable pore structure of the material.

Description

Preparation method of porous carbon fiber electromagnetic wave absorbing agent
Technical Field
The invention relates to a preparation method of a porous carbon fiber electromagnetic wave absorber, belonging to the technical field of microwave absorbing materials.
Background
With the rapid development of modern electronic information technology, the wide application of various electronic devices causes serious electromagnetic pollution to the environment. Electromagnetic pollution not only affects the normal activities of human beings, but also interferes with the normal operation of precision electronic components. In addition, in the military field, nowadays, the anti-stealth radar technology is more and more advanced, and the aircraft puts higher requirements on stealth coatings. Therefore, the research of the wave-absorbing material is widely regarded in the civil field and the military field. In recent years, wave-absorbing materials are developed in the directions of light weight, thin thickness, wide frequency band and strong absorption. Among them, ferrite, which is a conventional material, is still widely used.
However, ferrites do not meet increasingly stringent requirements: controllable electromagnetic parameters and light weight. The magnetic permeability of the ferrite is rapidly reduced along with the increase of the frequency, which greatly influences the wave absorbing performance of the ferrite, and the ferrite needs to reach the thickness of more than 2.0mm to obtain relatively good wave absorbing performance. For example, Fe was prepared by the Cao flourishing subject group of Beijing Phytology university3O4The @ C nanorod is researched and found that the composite shows the best absorption performance when the thickness is 2mm and the frequency is 14.96GHz, and the maximum reflection loss is-27.9 dB. (Y.J.Chen, G.Xiao, T.S.Wang, Q.Y.Ouyang, L.Y.Qi, Y.Ma, P.Gao, C.L.Zhu, M.S.Cao and H.B.jin, ports Fe3O4/carbon core/shell nanorods: synthesis and electronic properties.j.phys.chem.c, 2011, 115, 13603-; nanometer ring Fe with core-shell structure is prepared by the same country elegant subject group of Hubei Wuhan university3O4The compound is found to have a strongest absorption peak at 3.44GHz of-55.68 dB at a thickness of 6.2 mm. (T.Wu, Y.Liu, X.Zeng, T.cui, Y.ZHao, Y.Li and G.Tong, simple Hydrothermal Synthesis of Fe3O4C Core-Shell Nanorings for Efficient Low-Frequency Microwave absorption, ACSAppl, Mater, interfaces, 2016, 8, 7370-. In summary, the ferrite material exhibits good electromagnetic wave absorption performance as a wave-absorbing material, but the application of the material is greatly limited due to the narrow adjustable range of the electromagnetic parameters of the ferrite material, more importantly, the relatively high density, and particularly the current application to the flying with extremely high flying performanceThe device is arranged on the walking device.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a preparation method of a porous carbon fiber electromagnetic wave absorbing agent, which can obtain a porous and light electromagnetic wave absorbing material with adjustable electromagnetic parameters, wherein the electromagnetic wave absorbing material can show excellent absorption bandwidth under low thickness (1.9 mm).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a porous carbon fiber electromagnetic wave absorber comprises the following steps:
(1) sequentially adding PVP, ethyl orthosilicate and iron acetylacetonate into N, N-dimethylformamide, and stirring at high temperature until the PVP, the ethyl orthosilicate and the iron acetylacetonate are completely dissolved;
(2) putting the solution prepared in the step (1) into an injector, carrying out electrostatic spinning, collecting a product obtained after spinning, and drying the product in vacuum; calcining the dried product in argon;
(3) and (3) soaking the calcined product obtained in the step (2) in HF, performing centrifugal separation after soaking, and collecting the separated product.
Wherein the cross-sectional diameter of the obtained porous carbon fiber was 150 nm.
Wherein, in the step (1), VDMF+V TEos10 mL; the addition amount of PVP is 1.5-1.6 g, and the molecular weight of PVP is 130 ten thousand; the addition amount of the iron acetylacetonate is 1.25-1.28 g.
Wherein, in the step (1), the mixture is stirred at 85-90 ℃ until the mixture is completely dissolved.
Wherein in the step (2), the parameters of electrostatic spinning are as follows: the voltage is 16-17 kv, the vertical distance between the injector and the receiving plate is 15-16 cm, and the material pushing speed of the injector is 0.06-0.065 mL/h.
In the step (2), the calcining temperature is 700-750 ℃, the heat preservation time is 2-2.5 h, and the heating rate is 5-5.5 ℃/min.
Wherein in the step (3), the mass fraction of HF is 5-6 wt%, and the soaking time is 2-2.5 h.
Has the advantages that: compared with the traditional wave-absorbing material, the porous carbon fiber material prepared by the method has high absorption strength under low thickness, and the wave-absorbing performance of the material is adjustable due to the adjustable pore structure of the material; finally, the preparation method has simple process, does not need complex synthesis equipment, and can realize large-scale and large-batch production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a product obtained in example 1 of the present invention;
FIG. 2 is a TEM photograph of a porous carbon fiber obtained in example 1 of the present invention;
FIG. 3 is a reflection loss map of a porous carbon fiber prepared in example 1 of the present invention;
FIG. 4 shows the mixing ratio of the raw materials adjusted to VDMF：VTEOSReflection loss profile of porous carbon fiber prepared 8: 2.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
Example 1
The preparation method of the porous carbon fiber electromagnetic wave absorbing agent comprises the following steps:
step 1, adding 1.5g of PVP (molecular weight 130 ten thousand), 0.5mL of Tetraethoxysilane (TEOS) and 1.28g of iron acetylacetonate in sequence into 9.5mLN, N-Dimethylformamide (DMF), and stirring at 90 ℃ until the mixture is completely dissolved;
step 2, putting the solution prepared in the step 1 into a 10mL injector, setting electrostatic spinning parameters, collecting a product obtained after spinning, and drying the product in a vacuum drying oven for 12 hours; the parameters of electrostatic spinning are as follows: the voltage is 16kv, the vertical distance between the injector and the receiving plate is 15cm, and the pushing speed of the injector is 0.06 mL/h; finally, calcining the dried product in argon at 700 ℃, keeping the temperature for 2h and increasing the temperature at 5 ℃/min;
and 3, placing the calcined product obtained in the step 2 in HF with the mass fraction of 5 wt% for soaking for 2 hours, and performing centrifugal separation after soaking, wherein the product collected after separation is the porous carbon fiber.
The pore volume of the product obtained in example 1 was 0.49cm3G, when the mixing ratio of the raw materials is adjusted, the pore volume of the obtained product can be correspondingly changed, thereby affecting the final wave absorbing performance, for example, when the mixing ratio of the raw materials is adjusted to be VDMF：VTEosAt 8: 2, the pore volume of the product was 1.05cm3As can be seen from FIG. 4, the reflection loss of the product is above-7.0 dB at a large thickness of 5mm, but the product cannot meet the requirement of high loss at a low thickness.
Fig. 1 is an X-ray diffraction pattern of the porous carbon fibers obtained in examples 1 and 2 of the present invention, and it can be seen from fig. 1 that it is a typical X-ray diffraction pattern of carbon.
Fig. 2 is a TEM photograph of the porous carbon fiber obtained in example 1 of the present invention, and it can be seen from fig. 2 that the fiber diameter of the porous carbon fiber is about 150nm and a plurality of pore structures having non-uniform sizes are distributed inside the carbon fiber.
Fig. 3 is a graph of the reflection loss of the porous carbon fibers obtained in examples 1 and 2. As can be seen from FIG. 3, the product of example 1 shows excellent wave-absorbing performance, the reflection loss is as high as-43 dB under the thickness of 2.2mm, the bandwidth is 6.4GHz, and the bandwidth which is less than-10 dB under the thickness of 1.9mm can reach 4.2 GHz. When the mixing ratio of the raw materials is adjusted to VDMF：VTEosAt 8: 2, the product obtained has a reflection loss above-7.0 dB in the full band and at greater thicknesses.
The porous fiber wave-absorbing material is prepared by an electrostatic spinning method, and the porous carbon fiber has anisotropy, so that a large amount of electromagnetic waves are absorbed by the generation of surface polarization, and a conductive network is built among the fibers to improve the conductive loss and further strengthen the absorption of the electromagnetic waves. Therefore, the invention has good wave-absorbing performance under low thickness.

Claims (7)

1. A preparation method of a porous carbon fiber electromagnetic wave absorber is characterized by comprising the following steps:
(1) sequentially adding PVP, ethyl orthosilicate and iron acetylacetonate into N, N-dimethylformamide, and stirring at high temperature until the PVP, the ethyl orthosilicate and the iron acetylacetonate are completely dissolved;
(2) putting the solution prepared in the step (1) into an injector, carrying out electrostatic spinning, collecting a product obtained after spinning, and drying the product in vacuum; calcining the dried product in argon;
(3) and (3) soaking the calcined product obtained in the step (2) in HF, performing centrifugal separation after soaking, and collecting the separated product.
2. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: the cross-sectional diameter of the obtained porous carbon fiber is not less than 150 nm.
3. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: in step (1), VDMF+VTEOs10 mL; the addition amount of PVP is 1.5-1.6 g, and the molecular weight of PVP is 130 ten thousand; the addition amount of the iron acetylacetonate is 1.25-1.28 g.
4. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: in the step (1), stirring is carried out at 85-90 ℃ until the mixture is completely dissolved.
5. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: in the step (2), the parameters of electrostatic spinning are as follows: the voltage is 16-17 kv, the vertical distance between the injector and the receiving plate is 15-16 cm, and the material pushing speed of the injector is 0.06-0.065 mL/h.
6. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: in the step (2), the calcining temperature is 700-750 ℃, the heat preservation time is 2-2.5 h, and the heating rate is 5-5.5 ℃/min.
7. The method for preparing a porous carbon fiber electromagnetic wave absorber according to claim 1, characterized in that: in the step (3), the mass fraction of HF is 5-6 wt%, and the soaking time is 2-2.5 h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112702900A (en) * 2020-11-24 2021-04-23 南京航空航天大学 Metamaterial wave absorber
CN114717843A (en) * 2022-04-08 2022-07-08 富优特(山东)新材料科技有限公司 Flexible wave-absorbing composite material with adjustable performance and preparation method and application thereof

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CN102965766A (en) * 2012-11-14 2013-03-13 同济大学 New method for synthesizing nanometal particle-loaded carbon nanofiber
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CN103556304A (en) * 2013-10-28 2014-02-05 江苏大学 Ferrite nanofiber strip and preparation method thereof
CN103741263A (en) * 2014-01-15 2014-04-23 辽宁石油化工大学 Preparation method of high-specific-surface porous TiO2 nano-fiber
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CN105951218A (en) * 2016-04-21 2016-09-21 天津工业大学 Preparation of nano-carbon fiber with high specific surface area
CN106835364A (en) * 2017-01-19 2017-06-13 南京理工大学 A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ
CN109735962A (en) * 2018-12-26 2019-05-10 昆明冶金高等专科学校 A method of ferroferric oxide magnetic nano fiber is prepared in situ
CN110042500A (en) * 2018-01-15 2019-07-23 哈尔滨工业大学 A kind of preparation method of ferroso-ferric oxide/silica composite fiber microwave absorbing material
CN110894624A (en) * 2019-12-02 2020-03-20 陕西科技大学 Magnetic metal doped vanadium nitride nano composite fiber microwave absorbent and preparation method thereof

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US20150056471A1 (en) * 2012-02-16 2015-02-26 Cornell University Ordered porous nanofibers, methods, and applications
CN102965766A (en) * 2012-11-14 2013-03-13 同济大学 New method for synthesizing nanometal particle-loaded carbon nanofiber
CN103436995A (en) * 2013-08-05 2013-12-11 江苏科技大学 Fe/C composite nanofiber microwave absorbent, preparation method and application of absorbent
CN103556304A (en) * 2013-10-28 2014-02-05 江苏大学 Ferrite nanofiber strip and preparation method thereof
CN103741263A (en) * 2014-01-15 2014-04-23 辽宁石油化工大学 Preparation method of high-specific-surface porous TiO2 nano-fiber
CN105951218A (en) * 2016-04-21 2016-09-21 天津工业大学 Preparation of nano-carbon fiber with high specific surface area
CN106835364A (en) * 2017-01-19 2017-06-13 南京理工大学 A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ
CN110042500A (en) * 2018-01-15 2019-07-23 哈尔滨工业大学 A kind of preparation method of ferroso-ferric oxide/silica composite fiber microwave absorbing material
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112702900A (en) * 2020-11-24 2021-04-23 南京航空航天大学 Metamaterial wave absorber
CN114717843A (en) * 2022-04-08 2022-07-08 富优特(山东)新材料科技有限公司 Flexible wave-absorbing composite material with adjustable performance and preparation method and application thereof

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