CN115558304A - Preparation method of ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating - Google Patents

Preparation method of ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating Download PDF

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CN115558304A
CN115558304A CN202211183718.XA CN202211183718A CN115558304A CN 115558304 A CN115558304 A CN 115558304A CN 202211183718 A CN202211183718 A CN 202211183718A CN 115558304 A CN115558304 A CN 115558304A
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carbon fiber
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solid waste
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CN115558304B (en
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汪嘉恒
宫新宇
吴玉程
魏鑫
陈志远
吴运飞
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Hefei Maiwei New Material Technology Co ltd
Hefei University Of Technology Asset Management Co ltd
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    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked

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Abstract

The invention discloses a preparation method of an ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating, which is based on the one-dimensional characteristic of chopped carbon fiber waste and through the adjustment of the surface conductivity of carbon fibersAnd the insulating outer layer coating scheme is combined, so that the eddy current size on the surface of the carbon fiber is reduced, the shielding capability of a reverse magnetic field is improved, and macroscopic conductive connection caused by overlapping of one-dimensional carbon fibers is avoided. The material of the invention can be directly fused with a polymer matrix used by a device, and the integral resistivity can still be kept at 10 9 ‑10 20 The higher level of Ω · m can ensure the electrical safety and performance of surrounding connectors and circuits. The invention can be applied to electromagnetic wave shielding of DC-42.5 GHz frequency band in various devices and products.

Description

Preparation method of ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating
Technical Field
The invention belongs to the field of electromagnetic functional materials, and particularly relates to a preparation method of an ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating.
Background
Electromagnetic compatibility (EMC) of electrical products has become a mandatory standard for market entry in countries around the world. In the increasingly growing fields of electronics and communications, electromagnetic radiation generated by devices during operation and external electromagnetic interference become industry pain points which influence important factors such as product performance, reliability and safety, and the problems of the industry pain points are distributed in a plurality of key fields such as new energy automobiles, consumer electronics, intelligent internet of things products, communication products such as 5G and the like, wearable electronic products, aviation, aerospace and the like. For example, in a new energy automobile, multiband electromagnetic waves generated by densely distributed three-electric systems are mutually superposed, so that failures of a vehicle driving system and a sensor are easily caused, and driving safety is threatened; electromagnetic emissions from electronic components in the aircraft can affect the operation of radar, communication and sensing systems, leading to flight safety accidents; the intelligent Internet of things system receives the interference of external stray signals, so that the distortion of a sensor and a receiver is caused, the linkage of multiple devices is influenced, and even the collapse of the Internet of things is caused. Therefore, in response to the development of miniaturized and integrated devices, the key technology of the ultra-light and efficient electromagnetic shielding material needs to be solved.
The currently applied electromagnetic shielding materials are mainly focused on 1-18GHz frequency bands, especially 8-12GHz (X-band) and 5G frequency bands (C-band), and less electromagnetic shielding materials are suitable for a wide frequency range. The electromagnetic shielding mode aiming at the microwave frequency band is mainly conductive shielding, namely, the entrance and the influence of an external electromagnetic field are counteracted through a reverse magnetic field generated by the electromagnetic induction effect of a conductor in the microwave. In the industry, related products and devices are mainly provided with a metal conductive shielding shell or conductive paint for external overall shielding. However, the shielding design difficulty of the method for miniaturization and miniaturization devices is very large, and leakage waves still occur at key positions of connectors, connectors and the like, so that the current strict EMC standard and integration requirements cannot be met. The development of a novel insulating electromagnetic shielding material with high resistivity to enable the insulating electromagnetic shielding material to be seamlessly integrated with a device substrate and meet the requirement of electrical performance while ensuring the electromagnetic performance is considered to be a brand new solution for the EMC problem of future micro devices and special-shaped connectors.
Disclosure of Invention
The invention aims to solve the problems of the application of the current conductive shielding material in small and integrated devices, and provides a preparation method of an ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating. Based on the one-dimensional characteristic of the chopped carbon fiber waste, the invention not only reduces the eddy current size on the surface of the carbon fiber and improves the shielding capability of a reverse magnetic field, but also avoids macroscopic conductive connection caused by overlapping of the one-dimensional carbon fibers by modulating the surface conductivity of the carbon fiber and combining an insulating outer layer coating scheme. The material of the invention can be directly fused with a polymer matrix used by a device, and the overall resistivity can still be kept at 10 9 -10 20 The higher level of Ω · m can ensure the electrical safety and performance of surrounding connectors and circuits. The invention can be applied to electromagnetic wave shielding of DC-42.5 GHz frequency band in various devices and products.
The invention relates to a preparation method of an ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating, which is used for enhancing microscopic electromagnetic shielding and simultaneously cutting off macroscopic conductive transport by regulating and controlling the conductivity of the surface of chopped carbon fibers and combining with the coating of an insulating material, and specifically comprises the following steps:
step 1: uniformly dispersing 0.05-3g of cleaned chopped carbon fiber solid waste into 20ml of absolute ethyl alcohol, adding a certain amount of dispersing agent, continuously carrying out ultrasonic treatment for 0.5-3 h, and improving the charge distribution on the surface through functional groups to uniformly disperse the carbon fiber solid waste; then carrying out suction filtration or centrifugal separation to obtain modified chopped carbon fiber powder with good polar solution dispersibility;
step 2: dispersing 0.05-3g of modified chopped carbon fiber powder obtained in the step 1 into 10-50 mL of conductive polymer monomer solution with the concentration of 0.0001-1 g/mL, stirring for 1h until the solution is uniform, and adjusting the pH value of the system to be less than or equal to 5 to obtain a precursor solution;
and step 3: under continuous stirring, dropwise adding 3-10ml of initiator into the precursor solution obtained in the step 2, continuously stirring and reacting for 0.5-10 h under an ice bath condition, cleaning the obtained product by using distilled water and absolute ethyl alcohol, and performing suction filtration or centrifugal separation to obtain carbon fiber powder with the surface modified by the conductive polymer;
and 4, step 4: taking the carbon fiber powder with the modified conductive polymer surface obtained in the step 3, and respectively coating the particles with insulating amorphous silicon oxide or insulating polymer shell layers by adopting the step 4a or the step 4b:
4a: uniformly dispersing carbon fiber powder with the surface modified by a conductive polymer into a mixed solution consisting of water, alcohol and ammonia water, stirring at room temperature for 0.5-2 h, slowly dropwise adding tetraethyl orthosilicate (TEOS) into the system, and keeping the room temperature to continue stirring and reacting for 1-20 h; washing the reaction product with water and ethanol, filtering or centrifugally separating and drying to obtain the insulating amorphous SiO 2 Coated biomass carbon-based shielding material powder;
4b: uniformly dispersing carbon fiber powder modified by the surface of a conductive polymer in insulating polymer monomer aqueous solution with the concentration of 0.05-8 mol/L, stirring at room temperature for 0.5-5 h, slowly adding an initiator into the system, continuously stirring at 0-90 ℃ for reaction for 1-20 h, washing a reaction product by water and ethanol, and performing suction filtration or centrifugal separation and drying to obtain insulating polymer coated biomass carbon-based shielding material powder;
and 5: and (4) mixing the carbon fiber one-dimensional material coated by the insulating shell layer obtained in the step (4) with a device substrate, and forming to obtain the electromagnetic shielding material coated with high-resistivity insulation and the device.
The device substrate comprises resin, rubber, paint, colloid, paraffin and the like.
The adding mass of the carbon fiber one-dimensional material coated by the insulating shell layer is 10-50% of the mass of the device matrix.
The mixing mode comprises direct mixing, banburying or open mixing and the like.
Molding methods include injection molding, extrusion molding, compression molding, blow molding, extrusion, rotational molding, coating, and the like.
In the step 1, the length of the chopped carbon fiber is 0.5-3mm, and the diameter is 2-5um.
In the step 1, the dispersant may be one or more of polyvinylpyrrolidone (PVP), sodium dodecyl benzene sulfonate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), KH550, polyethylene glycol (PEG), oleic acid, tween and the like, or may be other types with affinity for the carbon fiber surface; the addition ratio of the dispersant is 0.001-3mol/L.
In step 2, reagents such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, etc. may be used for adjusting the pH.
In the step 2, the conductive polymer monomer is one or more of aniline, thiophene and pyrrole.
In step 3, the initiator is 0.02-4mol/L persulfate solution, or other agent capable of causing the polymerization of the monomer.
In step 4a, the volume ratio of ammonia water (with the concentration of 25-28 percent), water and alcohol in the mixed solution is 1:2 to 30:25 to 60.
In the step 4a, the proportion of the carbon fiber powder with the surface modified by the conductive polymer dispersed in the mixed solution is 0.01-0.075 g/mL.
In step 4a, the addition volume of tetraethyl orthosilicate is 2-20% of the volume of the total solution.
In step 4b, the insulating polymer monomer is selected from monomers constituting polymers with high resistivity, such as Polystyrene (PS), polymethyl methacrylate (PMMA), polyphenylene sulfide (PPS), polyamide (PA), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), polycarbonate (PC), polyoxymethylene (POM), polyethylene (PE), polyvinyl chloride (PVC), polylactic acid (PLA), and precursor monomers of doped or derivative thereof.
In the step 4b, the proportion of the carbon fiber powder modified by the conductive polymer surface dispersed in the insulating polymer monomer aqueous solution is 0.01-0.075 g/mL.
In step 4b, the initiator is persulfate or a reagent for polymerizing the monomers, and the addition volume of the initiator is 1-12% of the total solution volume.
The advantages and the beneficial effects of the invention are embodied in that:
1. according to the invention, the carbon fiber is coated by amorphous or polymer with insulating property to form a conductive/insulating one-dimensional heterostructure, so that an effective electromagnetic shielding effect is formed inside the structure, meanwhile, external conductive connection is avoided, and a novel insulating electromagnetic shielding matrix is constructed;
2. the invention modulates the reverse magnetic field of the eddy current in different frequency bands by surface modification of the conductive polymer intermediate layer, thereby modulating the surface impedance and the applicable frequency band of electromagnetic shielding, and the invention can cover electromagnetic shielding in a DC-42.5 GHz widely applied frequency band;
3. the high-resistivity composite material can be directly fused with a base material of a device and directly used as a raw material for forming a product or the device, so that an external metal shielding shell is replaced, the internal circuit insertion is not influenced, and the mechanical property of the device can be greatly improved by the carbon fiber-based material;
4. the carbon fiber solid waste is industrial waste generated in the production of carbon fiber related parts, the technology of the invention can enable the carbon fiber solid waste which is difficult to treat to obtain new application, saves the energy consumption of incineration, and has extremely low process cost, energy saving, economy and environmental protection.
Drawings
FIG. 1 is an SEM image of 1mm chopped carbon fiber/PANI/PS prepared in example 3; SEM appearance image shows that 0.5mm chopped carbon fiber/PANI/PS is cylindrical with the diameter of 5 mu m, the surface of the cylindrical is smooth and flat, which shows that the PANI/PS is coated on the surface of the carbon fiber in a double-layer compact and insulating way, and the PANI coated on the surface of the carbon fiber can be seen in the gap of the shell layer.
FIG. 2 is the 0.5mm chopped carbon fiber/PANI/SiO prepared in example 4 2 SEM image of (a); SEM appearance image shows that 1mm chopped carbon fiber/PANI/SiO 2 Is a column with the diameter of 5 mu m, the surface of the column is smooth and flat, which indicates PANI/SiO 2 The gap of the shell layer can be seen as PANI coated on the surface of the carbon fiber.
FIG. 3 shows real parts of dielectric constants of samples of examples 1 to 5 in (a) 1 to 18GHz, (b) 18 to 26.5GHz, and (c) 26.5 to 40GHz bands, respectively; examples 1-5 correspond to samples having epsilon' at higher levels in the 1-40GHz range, with a partial band of frequencies in the 1-18GHz range of up to 20 and up to 30, indicating the presence of a large number of dielectric dipoles in the biomass carbon and carbon fiber/PANI conductive cores despite the coating of the insulating shell.
FIG. 4 shows imaginary parts of dielectric constants of samples in (a) 1 to 18GHz, (b) 18 to 26.5GHz, and (c) 26.5 to 40GHz bands in examples 1 to 5, respectively; the values of epsilon "of the samples corresponding to examples 1-5 are also large at 1-40GHz, wherein the full frequency band reaches above 20 in the 1-40GHz band, wherein the frequency band reaches 200 in the 1-18GHz band, and up to 500, indicating that the chopped carbon fibers and the chopped carbon fiber/PANI conductive core have excellent dielectric loss performance despite being coated with the insulating shell, and the imaginary part is larger than the real part indicating that the conductive/insulating interface forms effective shielding so that electromagnetic waves are multiply reflected inside the carbon fibers.
FIG. 5 shows the shielding effectiveness of the samples of examples 1-5 in the frequency bands (a) 1-18GHz, (b) 18-26.5GHz, and (c) 26.5-40GHz, respectively. The SE of the high-resistivity insulation samples in examples 1-5 already exceeds 10dB in the C-Ku frequency band of 1-18GHz and the full frequency band of 18-26.5GHz, and exceeds 35dB in the partial frequency band of 26.5-40GHz, wherein the SE of the third example can reach 70dB at most. Higher resistivity (greater than 10) in combination with the samples of examples 1-5 9 Omega · m), which shows that the biomass carbon and the biomass carbon/PANI conductive core have higher dielectric property, so that the biomass carbon and the biomass carbon/PANI conductive core can still form excellent effective shielding for electromagnetic waves in a frequency range of 1-40GHz under the conditions of coating of the insulating shell and no conductive connection among particles. In the figure (a), example 6 shows the shielding effectiveness of the carbon fiber without the conductive core and the insulating material, and the comparative examples 1-5 show that the double coating of the conductive core/the insulating material does not reduce the shielding effectiveness of the material.
Detailed Description
Example 1:
(1) Cleaning and drying 0.3g of carbon fiber solid waste with the diameter of 5 mu m and the short cutting length of 0.5mm, uniformly dispersing the carbon fiber solid waste in 20mL of absolute ethyl alcohol, adding 1g of PVP and 0.3g of PEG, continuously carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration and separation;
(2) Dispersing the modified carbon fiber obtained in the step (1) in 20mL of 5mol/L styrene monomer aqueous solution, dropwise adding 0.5mL of 0.15mol/L ammonium persulfate aqueous solution into the solution under the condition of stirring in a 70 ℃ water bath, and continuously stirring for 3h; washing the product with water and absolute ethyl alcohol, and then drying the product in vacuum for 8 hours to obtain carbon fiber/PS powder;
(3) And (3) mixing the carbon fiber/PS powder obtained in the step (2) with paraffin in a ratio of 20% for molding, and testing the electromagnetic parameters and the shielding effectiveness of the carbon fiber/PS powder at 1-18GHz, 18-26.5GHz and 26.5-40 GHz.
Example 2:
(1) Cleaning and drying 0.3g of carbon fiber solid waste with the diameter of 5 mu m and the short cutting length of 1mm, uniformly dispersing the carbon fiber solid waste in 20mL of absolute ethyl alcohol, adding 1g of PVP and 0.3g of PEG into the carbon fiber solid waste, continuously carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration and separation;
(2) Dispersing the modified carbon fiber obtained in the step (1) in 20mL of absolute ethyl alcohol, adding 0.2g of PVP and 0.8mL of ammonia water into the solution, and stirring for 0.5h to be uniform; then slowly dropwise adding 0.3ml of tetraethyl orthosilicate (TEOS) into the solution, and continuously stirring for 5 hours; washing the product with water and absolute ethyl alcohol, and drying for 8h in vacuum to obtain carbon fiber/SiO 2 Powder;
(3) The carbon fiber/SiO obtained in the step (2) 2 Mixing the powder with paraffin in a ratio of 20% to form, and testing the electromagnetic parameters and shielding effectiveness of the powder at 1-18GHz, 18-26.5GHz and 26.5-40 GHz.
Example 3:
(1) Cleaning and drying 0.3g of carbon fiber solid waste with the diameter of 5 mu m and the short cut length of 0.5mm, uniformly dispersing the carbon fiber solid waste in 20mL of absolute ethyl alcohol, adding 1g of PVP and 0.3g of PEG into the carbon fiber solid waste, continuously carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration and separation;
(2) Adding 30mL of 1mol/L aniline aqueous solution into the modified carbon fiber powder obtained in the step (1), dropwise adding 5mL of 0.2mol/L hydrochloric acid solution into the modified carbon fiber powder, and continuously performing ultrasonic treatment for 1h;
(3) Slowly dripping 5ml of ammonium persulfate aqueous solution with the concentration of 1mol/L into the precursor solution in the step (2) under the condition of continuous stirring, and continuously stirring for 5 hours; washing the reaction product with water and absolute ethyl alcohol, filtering, separating and drying for 8 hours to obtain carbon fiber/PANI powder;
(4) Dispersing the carbon fiber/PANI powder obtained in the step (3) in 20mL of absolute ethyl alcohol, adding 0.2g of PVP and 0.8mL of ammonia water into the solution, and uniformly stirring; then slowly dripping 0.3ml of tetraethyl orthosilicate (TEOS) into the solution, and continuously stirring for 5 hours; washing the product with water and absolute ethyl alcohol, and drying for 8h in vacuum to obtain carbon fiber/PANI/SiO 2 Powder;
(5) Subjecting the carbon fiber/PANI/SiO obtained in the step (4) to 2 Mixing the powder with paraffin wax in a ratio of 20% to form, and testing the electromagnetic parameters and the shielding effectiveness of the powder at 1-18GHz, 18-26.5GHz and 26.5-40 GHz.
Example 4:
(1) Cleaning and drying 0.3g of carbon fiber solid waste with the diameter of 5 mu m and the short cutting length of 1mm, uniformly dispersing the carbon fiber solid waste in 20mL of absolute ethyl alcohol, adding 1g of PVP and 0.3g of PEG into the carbon fiber solid waste, continuously carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration and separation;
(2) Adding 30mL of 1mol/L aniline aqueous solution into the modified carbon fiber powder obtained in the step (1), dropwise adding 5mL of 0.2mol/L hydrochloric acid solution into the modified carbon fiber powder, and continuously performing ultrasonic treatment for 1h;
(3) Slowly dripping 5ml of ammonium persulfate aqueous solution with the concentration of 1mol/L into the precursor solution in the step (2) under the condition of continuous stirring, and continuously stirring for 5 hours; washing the reaction product with water and absolute ethyl alcohol, filtering, separating and drying for 8 hours to obtain carbon fiber/PANI powder;
(4) Dispersing the carbon fiber/PANI powder obtained in the step (3) into 20mL of styrene monomer aqueous solution with the concentration of 5mol/L, dropwise adding 0.5mL of 0.15mol/L ammonium persulfate aqueous solution into the solution under the condition of water bath stirring at 70 ℃, and continuously stirring for 3 hours; washing the product with water and absolute ethyl alcohol, and then drying the product in vacuum for 58h to obtain carbon fiber/PANI/PS powder;
(5) And (3) mixing the carbon fiber/PANI/PS powder obtained in the step (4) with paraffin according to a proportion of 20% for molding, and testing the electromagnetic parameters and the shielding effectiveness of the carbon fiber/PANI/PS powder at 1-18GHz, 18-26.5GHz and 26.5-40 GHz.
Example 5:
(1) Cleaning and drying 0.3g of carbon fiber solid waste with the diameter of 5 mu m and the short cut length of 3mm, uniformly dispersing the carbon fiber solid waste in 20mL of absolute ethyl alcohol, adding 1g of PVP and 0.3g of PEG into the carbon fiber solid waste, continuously carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration and separation;
(2) Adding 30mL of 1mol/L aniline aqueous solution into the modified carbon fiber powder obtained in the step (1), dropwise adding 5mL of 0.2mol/L hydrochloric acid solution into the modified carbon fiber powder, and continuously performing ultrasonic treatment for 1h;
(3) Slowly dripping 5ml of ammonium persulfate aqueous solution with the concentration of 1mol/L into the precursor solution in the step (2) under the condition of continuous stirring, and continuously stirring for 5 hours; washing the reaction product with water and absolute ethyl alcohol, filtering, separating and drying for 8 hours to obtain carbon fiber/PANI powder;
(4) And (4) dispersing the carbon fiber/PANI powder obtained in the step (3) into a mixed solution composed of 2ml of MMA, 18ml of distilled water and 50ml of absolute ethyl alcohol, adding 0.052g of ammonium persulfate into the solution, continuously stirring for 10 hours in a water bath environment at 70 ℃, cleaning a product with water and ethanol, and then drying for 8 hours in vacuum to obtain the carbon fiber/PANI/PMMA powder.
(5) And (3) mixing the carbon fiber/PANI/PMMA powder obtained in the step (4) with paraffin according to the proportion of 20% for molding, and testing the electromagnetic parameters and the shielding effectiveness of the carbon fiber/PANI/PMMA powder at 1-18GHz, 18-26.5GHz and 26.5-40 GHz.

Claims (10)

1. The preparation method of the ultralight composite electromagnetic shielding material based on carbon fiber solid waste modification and insulation coating is characterized by comprising the following steps of:
step 1: uniformly dispersing 0.05-3g of cleaned chopped carbon fiber solid waste into 20ml of absolute ethyl alcohol, adding a dispersing agent, continuously carrying out ultrasonic treatment for 0.5-3 h, and improving the surface charge distribution through functional groups to uniformly disperse the carbon fiber solid waste; then carrying out suction filtration or centrifugal separation to obtain modified chopped carbon fiber powder with good polar solution dispersibility;
step 2: dispersing 0.05-3g of modified chopped carbon fiber powder obtained in the step 1 into 10-50 mL of conductive polymer monomer solution with the concentration of 0.0001-1 g/mL, stirring for 1h until the solution is uniform, and adjusting the pH value of the system to be less than or equal to 5 to obtain a precursor solution;
and step 3: under continuous stirring, dropwise adding 3-10ml of initiator into the precursor solution obtained in the step 2, continuously stirring and reacting for 0.5-10 h under an ice bath condition, cleaning the obtained product by using distilled water and absolute ethyl alcohol, and performing suction filtration or centrifugal separation to obtain carbon fiber powder with the surface modified by the conductive polymer;
and 4, step 4: taking the carbon fiber powder with the modified conductive polymer surface obtained in the step 3, and coating the particles with insulating amorphous silicon oxide or an insulating polymer shell layer by adopting the method in the step 4a or 4b:
4a: uniformly dispersing carbon fiber powder with the surface modified by a conductive polymer into a mixed solution consisting of water, alcohol and ammonia water, stirring at room temperature for 0.5-2 h, slowly dropwise adding tetraethyl orthosilicate into the system, and keeping the room temperature to continue stirring and reacting for 1-20 h; washing the reaction product with water and ethanol, filtering or centrifugally separating and drying to obtain the insulating amorphous SiO 2 Coated biomass carbon-based shielding material powder;
4b: uniformly dispersing carbon fiber powder with the surface modified by a conductive polymer into an insulating polymer monomer aqueous solution with the concentration of 0.05-8 mol/L, stirring at room temperature for 0.5-5 h, slowly adding an initiator into the system, continuously stirring at 0-90 ℃ for reaction for 1-20 h, washing a reaction product by water and ethanol, and performing suction filtration or centrifugal separation and drying to obtain insulating polymer coated biomass carbon-based shielding material powder;
and 5: and (4) mixing the carbon fiber one-dimensional material coated by the insulating shell layer obtained in the step (4) with a device substrate, and forming to obtain the electromagnetic shielding material coated with high-resistivity insulation and the device.
2. The production method according to claim 1, characterized in that:
in the step 1, the length of the chopped carbon fiber is 0.5-3mm, and the diameter is 2-5um.
3. The method of claim 1, wherein:
in the step 1, the dispersant is one or more of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, KH550, polyethylene glycol, oleic acid and tween; the addition ratio of the dispersant is 0.001-3mol/L.
4. The method of claim 1, wherein:
in the step 2, the conductive polymer monomer is one or more of aniline, thiophene and pyrrole.
5. The method of claim 1, wherein:
in the step 3, the initiator is persulfate solution, and the addition amount is 0.02-4mol/L.
6. The method of claim 1, wherein:
in the step 4a, the volume ratio of ammonia water, water and alcohol in the mixed solution is 1:2 to 30:25 to 60.
7. The method of claim 1, wherein:
in the step 4a, the proportion of the carbon fiber powder with the surface modified by the conductive polymer dispersed in the mixed solution is 0.01-0.075 g/mL; the addition volume of the tetraethyl orthosilicate is 2-20% of the volume of the total solution.
8. The method of claim 1, wherein:
in step 4b, the insulating polymer monomer is selected from monomers constituting a polymer having a high resistivity of polystyrene, polymethylmethacrylate, polyphenylene sulfide, polyamide, polypropylene, polybutylene terephthalate, polyimide, polycarbonate, polyoxymethylene, polyethylene, polyvinyl chloride, or polylactic acid, and precursor monomers of a dopant or derivative thereof.
9. The production method according to claim 1, characterized in that:
in the step 4b, the proportion of the carbon fiber powder modified by the conductive polymer surface dispersed in the insulating polymer monomer aqueous solution is 0.01-0.075 g/mL.
10. The production method according to claim 1, characterized in that:
in the step 5, the adding mass of the one-dimensional carbon fiber material coated by the insulating shell layer is 10-50% of the mass of the device matrix.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150305212A1 (en) * 2012-10-16 2015-10-22 Università Degli Studi Di Roma "La Sapienza" Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences
CN106298001A (en) * 2016-08-12 2017-01-04 江苏亨通线缆科技有限公司 Electromagnetic wave shielding communication cable for track traffic
CN106479293A (en) * 2016-11-10 2017-03-08 无锡市明盛强力风机有限公司 A kind of carbon fiber electromagnetic screen coating
KR20170037005A (en) * 2015-09-25 2017-04-04 재단법인 한국탄소융합기술원 Flexible and thin film for shielding from electric wave and fabrication method for the same
CN106671502A (en) * 2017-01-16 2017-05-17 华南理工大学 Short carbon fiber based electromagnetic shielding composite material and preparation method thereof
CN107541996A (en) * 2016-06-25 2018-01-05 董晓 A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper
CN113999489A (en) * 2021-11-09 2022-02-01 齐盛时代(广州)科技有限公司 High-power microwave resistant shielding film and preparation method thereof
CN114369955A (en) * 2021-12-30 2022-04-19 山东仁丰特种材料股份有限公司 Method for preparing high-performance electromagnetic shielding paper by using carbon fibers
WO2022084002A1 (en) * 2020-10-21 2022-04-28 Totalenergies Onetech Composite material with emi shielding properties and process to produce it
CN114874591A (en) * 2022-06-20 2022-08-09 中国船舶重工集团公司第七二五研究所 Conductive super-crosslinked conjugated polymer electromagnetic wave absorption material and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150305212A1 (en) * 2012-10-16 2015-10-22 Università Degli Studi Di Roma "La Sapienza" Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences
KR20170037005A (en) * 2015-09-25 2017-04-04 재단법인 한국탄소융합기술원 Flexible and thin film for shielding from electric wave and fabrication method for the same
CN107541996A (en) * 2016-06-25 2018-01-05 董晓 A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper
CN106298001A (en) * 2016-08-12 2017-01-04 江苏亨通线缆科技有限公司 Electromagnetic wave shielding communication cable for track traffic
CN106479293A (en) * 2016-11-10 2017-03-08 无锡市明盛强力风机有限公司 A kind of carbon fiber electromagnetic screen coating
CN106671502A (en) * 2017-01-16 2017-05-17 华南理工大学 Short carbon fiber based electromagnetic shielding composite material and preparation method thereof
WO2022084002A1 (en) * 2020-10-21 2022-04-28 Totalenergies Onetech Composite material with emi shielding properties and process to produce it
CN113999489A (en) * 2021-11-09 2022-02-01 齐盛时代(广州)科技有限公司 High-power microwave resistant shielding film and preparation method thereof
CN114369955A (en) * 2021-12-30 2022-04-19 山东仁丰特种材料股份有限公司 Method for preparing high-performance electromagnetic shielding paper by using carbon fibers
CN114874591A (en) * 2022-06-20 2022-08-09 中国船舶重工集团公司第七二五研究所 Conductive super-crosslinked conjugated polymer electromagnetic wave absorption material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
喻冬秀;陈明涛;皮丕辉;文秀芳;程江;杨卓如;: "聚苯胺包覆短碳纤维的制备及电磁性能研究", 高校化学工程学报, no. 01, pages 2 *
喻冬秀等: "电磁屏蔽涂料用改性短碳纤维的研究", 《化工新型材料》, vol. 35, no. 3, pages 165 *

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