CN113444357B - Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material - Google Patents
Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material Download PDFInfo
- Publication number
- CN113444357B CN113444357B CN202110849943.1A CN202110849943A CN113444357B CN 113444357 B CN113444357 B CN 113444357B CN 202110849943 A CN202110849943 A CN 202110849943A CN 113444357 B CN113444357 B CN 113444357B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- solution
- composite material
- dopamine
- regenerated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0843—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a preparation method of a flexible regenerated carbon fiber electromagnetic shielding composite material, which is characterized in that a regenerated carbon fiber is subjected to self-assembly of a metal organic framework and a carbon nano tube through a hydrothermal reaction by utilizing a dopamine polymerization surface modification method, and the carbon nano tube/regenerated carbon fiber composite material uniformly loaded with nano magnetic metal particles @ porous carbon is obtained after carbonization. And carrying out vacuum filtration on the obtained composite material under the condition of a magnetic field to form a film, impregnating and backfilling with resin, and carrying out heat treatment to obtain the flexible regenerated carbon fiber electromagnetic shielding composite material. The regenerated carbon fiber is subjected to high-temperature cracking, and is more suitable for surface treatment and conductivity regulation than the conventional sizing carbon fiber. Compared with the prior art, the method effectively regulates and controls the orientation control, the composite material interface structure and the electromagnetic shielding efficiency by carrying out high-value functional recycling on the regenerated carbon fibers recovered by pyrolyzing the waste composite material at high temperature.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding, and particularly relates to a preparation method of a flexible regenerated carbon fiber electromagnetic shielding composite material.
Background
With the continuous change of the electronic information era, the application range of electromagnetic waves in information transmission is further expanded in order to meet the requirement of obtaining high-speed information transmission. The pollution of electromagnetic wave radiation has many negative effects on human living environment, confidential military, business, communication and other fields. How to prevent and reduce electromagnetic radiation pollution and interference has attracted extensive attention from countries around the world. The electromagnetic wave radiation shielding materials currently used mainly include two major types, reflection type and absorption type. The nano-structure carbon material has rich active sites, high surface area and low density, and is a good electromagnetic wave absorption material; the defects that the common metal electromagnetic shielding material has high density, is easy to corrode in special environment and the like are overcome. However, carbon materials such as carbon fiber and carbon nanotube have low magnetic permeability, and cannot achieve the effect of absorbing electromagnetic waves to prevent secondary pollution. The surface of the carbon fiber is smooth and inert, so that the interface covalent bond of the composite material is lacked, and the bonding strength is low; when the composite material is compounded with other substrates, the interface performance of the composite material is improved by methods such as pretreatment, activation, coarsening and the like. Surface treatments generally include oxidation, plasma treatment, gamma ray treatment, surface metallization, and the like; the dopamine autopolymerization reaction condition is mild, the modified matrix structure is not influenced, a green and efficient functional platform is constructed on the surface of the matrix, and the method is an energy-saving and environment-friendly surface modification method.
Patent application CN201911383063.9 discloses a modified carbon fiber, wherein Dopamine (DA) is used for carrying out surface modification on a filler, so that the filler is uniformly dispersed and not agglomerated in a liquid phase; then the filler is efficiently and uniformly grafted on the surface of the carbon fiber by utilizing the Schiff base reaction principle; and finally, carrying out high-temperature carbonization treatment on the carbon fiber with the surface grafted with the filler by utilizing the principle that polydopamine is carbonized at high temperature to form a graphene-like layer structure, wherein the polydopamine on the surfaces of the carbon fiber and the filler is converted into graphene-like layer carbide with excellent conductivity in the process, so that the surface of the carbon fiber can be firmly coated with the filler to form an integral structure, the surface conductivity of the carbon fiber can be obviously improved, various loss mechanisms are formed on electromagnetic waves, and the electromagnetic shielding performance of the finally obtained modified carbon fiber is further enhanced. However, the patent adopts a blending method to add the filler, and the magnetic filler formed by self-assembly and carbonization of the regular crystal structure has higher uniformity, stability, polarization and magnetization loss. In addition, the raw materials adopted in the patent are not waste recycled carbon fibers, so the invention has the important significance of environmental protection with low cost.
The carbon fiber is used as a novel high-strength and high-modulus fiber material with the carbon content of more than 95 percent, has the characteristics of high specific strength, ultrahigh temperature resistance, fatigue resistance and the like, and is often used as a reinforcement of a thermosetting or thermoplastic resin composite material; the method is used in the national defense field of aerospace and the like and the civil field of automobiles, electronic devices and the like. However, because the fiber reinforced composite material is difficult to decompose, environmental pollution and resource waste caused by some waste composite materials become serious environmental, social and economic problems in China. However, in the prior art, the interface structure and the electromagnetic shielding effectiveness of the relevant waste recycled carbon fiber composite material are rarely studied.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a flexible regenerated carbon fiber electromagnetic shielding composite material, which can solve the problems of electromagnetic wave radiation pollution, low absorption effect, high density, low flexibility, easy corrosion and the like of the existing electromagnetic shielding material, and can recycle the waste carbon fiber reinforced composite material, regulate and optimize orientation and interface.
The purpose of the invention can be realized by the following technical scheme: a preparation method of a flexible regenerated carbon fiber electromagnetic shielding composite material comprises the following steps:
preparing regenerated carbon fibers coated with a polydopamine layer by using a dopamine solution soaking method to obtain dopamine modified regenerated carbon fibers, introducing active groups on the surfaces of the regenerated carbon fibers to improve the condition of smoothness and inertia of the surfaces of the regenerated carbon fibers, and cleaning and drying the regenerated carbon fibers to obtain the dopamine modified regenerated carbon fibers;
modifying the surface of the carbon nano tube by utilizing a dopamine oxidation polymerization method to obtain the carbon nano tube coated with a dopamine layer, namely a dopamine modified carbon nano tube;
mixing a surfactant, an organic ligand, dopamine modified regenerated carbon fibers, dopamine modified carbon nanotubes and an organic solvent, adding the mixture into a metal salt solution, stirring and mixing for 1-2h, carrying out hydrothermal reaction in a reaction kettle, washing, centrifuging and drying after the reaction is finished, and carrying out high-temperature carbonization treatment on the obtained product at 500-900 ℃ in a protective gas atmosphere to obtain the carbon nanotube/regenerated carbon fiber composite material uniformly loaded with nano magnetic metal particles @ porous carbon;
and carrying out vacuum filtration on the obtained product under the condition of a magnetic field to form a film, impregnating and backfilling the film with resin, and carrying out heat treatment to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
Furthermore, the regenerated carbon fiber is short-cut regenerated carbon fiber prepared by pyrolysis of a carbon fiber composite material, or short-cut regenerated carbon fiber prepared by cutting short regenerated carbon fiber prepared by pyrolysis of a carbon fiber composite material, the length of the short-cut regenerated carbon fiber is 3-8mm, the surface of the short-cut regenerated carbon fiber is in an inert smooth state, and no sizing agent exists.
Further, the regenerated carbon fiber is subjected to dopamine surface modification treatment, and the specific steps are as follows:
(11) adding the Tris into ionic water for dissolving to obtain Tris solution, namely Tris solution, wherein the concentration range of the Tris solution is 10-20mmol/L, and dropwise adding acid solution to adjust the pH value to 8-8.5;
(12) preparing a dopamine solution by using the Tris solution prepared in the step (11), soaking the short-cut regenerated carbon fibers in the dopamine solution, and taking out the short-cut regenerated carbon fibers, wherein the concentration range of the dopamine solution is 2-4mg/mL, and the soaking time of the carbon fibers is 24-48 h;
(13) and (3) washing the reaction product obtained in the step (12) with deionized water for multiple times until the filtrate is colorless and clear, centrifuging and then placing in a vacuum oven for drying to obtain the dopamine modified regenerated carbon fiber, wherein the temperature of the oven is 50-100 ℃, and the drying time is 24-36 h.
Further, the specific preparation method of the dopamine modified carbon nanotube comprises the following steps:
(21) adding the Tris into ionic water for dissolving to obtain Tris solution, namely Tris solution, wherein the concentration range of the Tris solution is 10-20mmol/L, and dropwise adding acid solution to adjust the pH value to 8-8.5;
(22) adding carbon nanotubes into a solvent, and uniformly dispersing by ultrasonic, wherein the carbon nanotubes are single-walled or multi-walled carbon nanotubes, and the solvent is deionized water or alcohol or a mixed solution of the deionized water and the alcohol;
(23) adding dopamine with mass into the mixed solution obtained in the step (22), then adding the solution obtained in the step (21), and stirring for 4-8 hours to prepare a dopamine solution, wherein the mass concentration of the dopamine solution is 1-4 mg/mL;
(24) and (4) washing the product obtained in the step (23) with deionized water for multiple times until the filtrate is colorless and clear, centrifuging, and drying in a vacuum oven at the temperature of 50-100 ℃ for 24-36h to obtain the dopamine modified carbon nanotube.
Further, the metal salt solution adopted in the preparation of the carbon nanotube/regenerated carbon fiber composite material uniformly loaded with the nano magnetic metal particles @ porous carbon is as follows: the nickel salt and/or cobalt salt are dissolved in an organic solvent to prepare the nickel salt/cobalt salt composite material, wherein the molar ratio of the nickel salt to the cobalt salt is 1: 0. 2: 1. 1: 1. 1: 2 or 0: 1.
further, the nickel salt and the cobalt salt are nitrate or acetate;
the organic solvent is one or a mixture of ethanol and N, N-dimethylformamide.
Further, the organic ligand is one of dimethyl imidazole, terephthalic acid and trimesic acid. The surfactant includes polyvinylpyrrolidone and the like.
Further, the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 20-40 h.
Further, the carbonization time is 2-4h, and the heating rate is 5-10 ℃/min.
Further, the vacuum filtration film-forming process is placed under a magnetic field, and the obtained magnetic short-cut regenerated carbon fiber composite material is subjected to orientation treatment;
the resin adopted by the impregnation backfilling is thermoplastic polyurethane, polyimide or acrylonitrile-butadiene-styrene copolymer (ABS); the heat treatment temperature is 100-350 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the carbon fiber adopted by the invention is regenerated chopped carbon fiber prepared by pyrolysis of waste carbon fiber composite material, the surface of the regenerated chopped carbon fiber is modified by dopamine, and a metal organic framework is loaded to be used as a template for preparing the magnetic nano structure @ nano porous carbon composite material.
(2) And performing functional composite regulation and control on the regenerated carbon fiber, and recycling the regenerated carbon fiber at a high value. The carbon fiber recovered by pyrolysis of the waste composite material is more suitable for surface treatment and conductivity regulation than the conventional sizing carbon fiber. The dopamine modification is carried out on the surfaces of the regenerated carbon fibers and the carbon nano tubes, the dopamine autopolymerization reaction condition is green and mild, the modified matrix structure is not influenced, and an efficient connecting functional platform is constructed on the surface of the matrix. And then mixing a surfactant, an organic ligand, dopamine modified regenerated carbon fibers, dopamine modified carbon nanotubes and an organic solvent, adding the mixture into a metal salt solution, constructing a metal organic framework self-assembly structure, uniformly loading the self-assembly structure on a carbon material, simply carbonizing the metal organic framework in one step to form a large number of porous carbon structures, wherein nano magnetic metal particles in a crystal structure have high dispersion uniformity, and the surface of nanoparticles in the structure is coated with a graphite carbon layer obtained by reduction, so that the oxidation of the nanoparticles can be effectively prevented, and the structure and the performance of the metal organic framework are diversified and adjustable due to the high porosity and the internal specific surface area of the metal organic framework. Endows the composite material with light weight, high-efficiency electromagnetic wave absorption and composite regulation and control performance of functions.
(3) The carbon fiber electromagnetic shielding composite material prepared by the invention has high chemical homogeneity, stability, lightness, thinness, flexibility and high electromagnetic shielding efficiency, overcomes the defects of the existing metal electromagnetic shielding material, and can be applied to more fields. The chemical synthesis technical route provided by the invention can be used as a beneficial reference for uniform modification and performance regulation of the surface of the carbon fiber.
Detailed Description
The present invention is further described with reference to the following examples, which are implemented on the premise of the technical solution of the present invention, and give detailed implementation methods and specific operation procedures, but the scope of the present invention is not limited to the following implementation examples.
In order to solve the electromagnetic wave radiation pollution, the existing electromagnetic shielding material has the defects of low absorption effect, high density, low flexibility, easy corrosion and the like, and the waste carbon fiber reinforced composite material is recycled, and the orientation and the interface are regulated, controlled and optimized. The invention provides a preparation method of a flexible regenerated carbon fiber electromagnetic shielding composite material, which obtains an electromagnetic shielding material with high electromagnetic shielding efficiency, light weight and flexibility, and adopts the following preparation method and technical route:
(1) the regenerated carbon fiber coated with the polydopamine layer is prepared by a method of soaking the regenerated carbon fiber in a dopamine solution, and active groups are introduced into the surface of the regenerated carbon fiber, so that the condition that the surface of the regenerated carbon fiber is smooth and inert is improved. And cleaning and drying to obtain the dopamine modified regenerated carbon fiber.
The regenerated carbon fiber is a regenerated short carbon fiber prepared by pyrolysis of a carbon fiber composite material. The length is 3-8mm, the surface is in an inert smooth state, and no sizing agent exists.
The carbon fiber dopamine surface modification treatment process comprises the following specific steps:
(11) weighing a certain mass of Tris (hydroxymethyl) aminomethane (Tris), adding deionized water into a volumetric flask for dissolving to obtain a Tris solution, optionally adding an acid solution dropwise to adjust the pH value to about 8-8.5, wherein the concentration range of the Tris solution is 10-20 mmol/L.
(12) Preparing a dopamine solution by using a Tris solution, and taking out the chopped regenerated carbon fibers after soaking in the dopamine solution. Optionally, the concentration of the dopamine solution ranges from 2mg/mL to 4mg/mL, and the carbon fiber soaking time is 24 hours to 48 hours.
(13) Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and centrifuging and then placing in a vacuum oven for drying to obtain the regenerated carbon fiber subjected to dopamine surface modification treatment. Optionally, the oven temperature is 50-100 ℃, and the drying time is 24-36 h.
(2) Modifying the surface of the carbon nano tube by utilizing a dopamine oxidation polymerization method, and washing and drying to obtain the carbon nano tube coated with the dopamine layer.
The surface modification treatment of the carbon nano tube dopamine comprises the following specific steps:
(21) weighing a certain mass of Tris, dissolving in a volumetric flask, optionally, dropwise adding an acid solution to adjust the pH value to about 8-8.5, wherein the concentration range of the Tris solution is 10-20 mmol/L.
(22) Weighing a proper amount of carbon nano tubes, and adding the carbon nano tubes into a reactor filled with a solvent; the carbon nano tube is dispersed in the solvent by ultrasonic evenly. Optionally, the carbon nanotube is a single-walled or multi-walled carbon nanotube, and the solvent is deionized water or alcohol or a mixed solution of the deionized water and the alcohol;
(23) and (5) adding a certain mass of dopamine into the mixed solution obtained in the step (22), adding the Tris solution prepared in the step (11) to prepare a dopamine solution, wherein optionally, the mass concentration of the dopamine solution is 1-4mg/mL, and the magneton stirring time is 4-8 hours.
(24) Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and centrifuging and then placing in a vacuum oven for drying to obtain the dopamine surface modified carbon nano tube. Optionally, the oven temperature is 50-100 deg.C, and the drying time is 24-36 h.
(3) Preparing the carbon nano tube/regenerated carbon fiber composite material loaded with the nano magnetic metal particles @ porous carbon.
The solution 1 is a mixed solution of nickel salt, cobalt salt and an organic solvent, optionally, the nickel salt and the cobalt salt are nitrate or acetate, and the molar ratio of the nickel salt to the cobalt salt is 1: 0. 2: 1. 1: 1. 1: 2. 0: 1, etc.; optionally, the organic solvent is one or a mixture of ethanol, N-Dimethylformamide (DMF). The organic ligand is one of dimethyl imidazole, terephthalic acid and trimesic acid;
the solution 2 is a mixed solution of a surfactant, an organic ligand, the dopamine modified regenerated carbon fiber obtained in the step (1), the dopamine modified carbon nanotube obtained in the step (2) and an organic solvent; optionally, the surfactant PVP has a mass of 2.4-3.6 g; the molar weight of the organic ligand is 16-20 mmol; the volume of the organic solvent is 100-150 mL.
Mixing and stirring the solution 1 and the solution 2 for a period of time, and adding the mixture into a reaction kettle for hydrothermal reaction; optionally, the mixing and stirring time of the solution 1 and the solution 2 is 1-2 h; the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 20-40 h;
and after the reaction is finished, washing, centrifuging and drying, and carrying out high-temperature carbonization treatment on the obtained product in a protective gas atmosphere to obtain the carbon nano tube/regenerated carbon fiber composite material loaded with the nano magnetic metal particles @ porous carbon. Optionally, the carbonization temperature is 500-900 ℃, the carbonization time is 2-4h, the heating rate is 5-10 ℃/min, and optionally, the washing solvent is deionized water or ethanol.
(4) Carrying out orientation vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling with resin, and performing heat treatment to obtain the flexible regenerated recycled carbon fiber electromagnetic shielding composite material.
The vacuum filtration film forming process is carried out under a magnetic field, and the magnetic short-cut regenerated carbon fiber is subjected to orientation treatment. Optionally, the impregnation encapsulating resin is thermoplastic polyurethane or polyimide or acrylonitrile-butadiene-styrene copolymer (ABS); the heat treatment temperature is 100-350 ℃.
Example 1
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolution to obtain a Tris solution of 12mmol/L, and adding a plurality of drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 3mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 30 hours at room temperature, and taking out the short-cut regenerated carbon fibers. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the ultrasonic wave. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. And obtaining the dopamine surface modified carbon nano tube.
Dissolving the dopamine modified regenerated carbon fiber and the dopamine modified carbon nanotube in 200mL of ethanol solution, stirring for 6h, and collecting reaction products through centrifugation and washing; and (5) placing the mixture in a vacuum oven for drying, wherein the oven temperature is 70 ℃, and the drying time is 12 h. And carrying out high-temperature carbonization treatment on the obtained carbon fiber product at 600 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube-loaded chopped carbon fiber. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The flexible recycled carbon fiber composite material obtained in example 1 was subjected to an electromagnetic shielding effectiveness test, and the shielding performance in the X-band (8-12GHz) was 18.5dB.
Example 2
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolving to obtain a Tris solution of 12mmol/L, and adding several drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40h at room temperature, and taking out. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
3mmol of nickel nitrate and 6mmol of cobalt nitrate were weighed and dissolved in 100mL of ethanol solution, and the solution was recorded as solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid and a proper amount of dopamine modified regenerated carbon fiber, dissolving in 100mL of ethanol solution, recording as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and sealing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for 24 hours to perform hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) drying in a vacuum oven at 70 ℃ for 12 h. And carbonizing the obtained carbon fiber product at the high temperature of 600 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the chopped carbon fiber loaded with the nano-magnetic metal particles @ porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The flexible recycled carbon fiber composite material obtained in the example 2 is subjected to an electromagnetic shielding effectiveness test, and the shielding performance in an X-band (8-12GHz) reaches 24.5dB.
Example 3
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolution to obtain a Tris solution of 12mmol/L, and adding a plurality of drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40 hours at room temperature, and taking out the short-cut regenerated carbon fibers. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the oven temperature is 70 ℃, and the drying time is 24 hours. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the ultrasonic wave. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. And obtaining the dopamine surface modified carbon nano tube.
3mmol of nickel nitrate and 6mmol of cobalt nitrate were weighed and dissolved in 100mL of ethanol solution, and the solution was recorded as solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid, a proper amount of dopamine modified regenerated carbon fiber and dopamine modified carbon nano-tubes, dissolving in 100mL of ethanol solution, marking as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and then placing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for sealing for 24 hours to carry out hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) placing the mixture in a vacuum oven for drying, wherein the oven temperature is 70 ℃, and the drying time is 12 h. And carbonizing the obtained carbon fiber product at the high temperature of 600 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube/chopped carbon fiber composite material loaded with the nano-magnetic metal particles and the porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The electromagnetic shielding effectiveness test of the flexible recycled carbon fiber composite material obtained in the embodiment 3 is carried out, and the shielding performance in an X wave band (8-12GHz) is 32-34dB.
Example 4
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolving to obtain a Tris solution of 12mmol/L, and adding several drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40 hours at room temperature, and taking out the short-cut regenerated carbon fibers. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the ultrasonic wave. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. And obtaining the dopamine surface modified carbon nano tube.
4.5mmol of nickel nitrate and 4.5mmol of cobalt nitrate were weighed and dissolved in 100mL of ethanol solution, and the solution was designated as solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid, a proper amount of dopamine modified regenerated carbon fiber and dopamine modified carbon nano-tubes, dissolving in 100mL of ethanol solution, marking as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and then placing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for sealing for 24 hours to carry out hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) placing the mixture in a vacuum oven for drying, wherein the oven temperature is 70 ℃, and the drying time is 12 h. And carbonizing the obtained carbon fiber product at the high temperature of 600 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube/chopped carbon fiber composite material loaded with the nano-magnetic metal particles and the porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; thermoplastic polyurethane is used for impregnation and backfilling, and the flexible regenerated recycled carbon fiber electromagnetic shielding composite material is obtained after heat treatment at 100 ℃ in an oven.
The flexible recycled carbon fiber composite material obtained in the embodiment 4 is subjected to an electromagnetic shielding effectiveness test, and the shielding performance in an X-wave band (8-12GHz) is 30-32dB.
Example 5
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolving to obtain a Tris solution of 12mmol/L, and adding several drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40h at room temperature, and taking out. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the ultrasonic wave. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. And obtaining the dopamine surface modified carbon nano tube.
6mmol of nickel nitrate and 3mmol of cobalt nitrate are weighed and dissolved in 100mL of ethanol solution, and the solution is recorded as a solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid, a proper amount of dopamine modified regenerated carbon fiber and dopamine modified carbon nano-tubes, dissolving in 100mL of ethanol solution, marking as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and then placing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for sealing for 24 hours to carry out hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) placing the mixture in a vacuum oven for drying, wherein the oven temperature is 70 ℃, and the drying time is 12 h. And carbonizing the obtained carbon fiber product at the high temperature of 600 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube/chopped carbon fiber composite material loaded with the nano-magnetic metal particles and the porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The flexible recycled carbon fiber composite material obtained in the example 5 is subjected to an electromagnetic shielding effectiveness test, and the shielding performance in an X-band (8-12GHz) reaches 35-36dB.
Example 6
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolution to obtain a Tris solution of 12mmol/L, and adding a plurality of drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40h at room temperature, and taking out. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the ultrasonic wave. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. Obtaining the dopamine surface modified carbon nano tube.
6mmol of nickel nitrate and 3mmol of cobalt nitrate were weighed and dissolved in 100mL of ethanol solution, and the solution was recorded as solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid, a proper amount of dopamine modified regenerated carbon fiber and dopamine modified carbon nano-tubes, dissolving in 100mL of ethanol solution, marking as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and then placing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for sealing for 24 hours to carry out hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) drying in a vacuum oven at 70 ℃ for 12 h. And carbonizing the obtained carbon fiber product at 700 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube/chopped carbon fiber composite material loaded with the nano-magnetic metal particles and the porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The flexible recycled carbon fiber composite material obtained in example 6 was subjected to an electromagnetic shielding effectiveness test, and the shielding performance in the X-band (8-12GHz) reached 40.3dB.
Example 7
Weighing 0.01mol of Tris, adding deionized water into a volumetric flask for dissolution to obtain a Tris solution of 12mmol/L, and adding a plurality of drops of concentrated hydrochloric acid to adjust the pH value to about 8.5; preparing a dopamine solution with the mass concentration of 4mg/mL by using a Tris buffer solution, soaking the short-cut regenerated carbon fibers in the dopamine solution for 40h at room temperature, and taking out. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; and (4) centrifuging, and drying in a vacuum oven at 70 ℃ for 24 h. And obtaining the regenerated carbon fiber subjected to dopamine surface modification treatment.
Weighing a proper amount of carbon nanotubes, and adding the carbon nanotubes into a beaker containing alcohol; the carbon nano-tube is dispersed evenly in the solution by ultrasonic. Adding a certain mass of dopamine and Tris buffer solution into a beaker to prepare a dopamine solution with the mass concentration of 2mg/mL, and stirring for 6 hours by using magnetons. Washing the reaction product with deionized water for many times until the filtrate is colorless and clear; after centrifugation, the mixture is placed in a vacuum oven for drying, the temperature of the oven is 70 ℃, and the drying time is 12 h. And obtaining the dopamine surface modified carbon nano tube.
5.6mmol of nickel nitrate and 2.4mmol of cobalt nitrate were weighed and dissolved in 100mL of ethanol solution, and the solution was designated as solution 1. Weighing 2.4g of polyvinylpyrrolidone (PVP, K30), 20mmol of 1, 4-phthalic acid, a proper amount of dopamine modified regenerated carbon fiber and dopamine modified carbon nano-tubes, dissolving in 100mL of ethanol solution, marking as solution 2, mixing and stirring the solution 1 and the solution 2 uniformly, and then placing the transparent solution in a stainless steel hydrothermal kettle at 150 ℃ for sealing for 24 hours to carry out hydrothermal reaction. Collecting the reaction product by centrifugation and washing; and (5) placing the mixture in a vacuum oven for drying, wherein the oven temperature is 70 ℃, and the drying time is 12 h. And carbonizing the obtained carbon fiber product at 800 ℃ for 3h in a protective gas atmosphere at the heating rate of 5 ℃/min to obtain the carbon nanotube/chopped carbon fiber composite material loaded with the nano-magnetic metal particles and the porous carbon. Carrying out vacuum filtration on the obtained chopped carbon fiber product under the condition of a magnetic field to form a film; and (3) impregnating and backfilling thermoplastic polyurethane, and carrying out heat treatment at 100 ℃ in an oven to obtain the flexible regenerated and recycled carbon fiber electromagnetic shielding composite material.
The flexible recycled carbon fiber composite material obtained in example 6 was subjected to an electromagnetic shielding effectiveness test, and the shielding performance in the X-band (8-12GHz) reached 43dB.
The results are shown in table 1 below:
TABLE 1
A PNA-X N5244a network analyzer is used for testing S parameters based on a waveguide method, and the testing frequency band is 8-12GHz of an X-wave band.
The conductivity of the electromagnetic shielding material was tested by a four-probe method (RTS-8, four-probe technologies, Inc., Guangzhou).
An Instro-1121 type material testing machine is adopted, and the stretching speed is 500 mm/min; tensile strength and elongation at break were obtained.
According to analysis of test results, the regenerated carbon fiber electromagnetic shielding composite material has effective electromagnetic shielding effectiveness, which is benefited by a porous carbon structure in the composite material and a large amount of uniformly distributed active nanoparticles loaded; the flexibility is good; has the important significance of environmental protection and low cost.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the flexible regenerated carbon fiber electromagnetic shielding composite material is characterized by comprising the following steps of:
preparing the regenerated carbon fiber coated with the polydopamine layer by using a method of soaking the regenerated carbon fiber in a dopamine solution to obtain dopamine modified regenerated carbon fiber;
modifying the surface of the carbon nano tube by utilizing a dopamine oxidation polymerization method to obtain the carbon nano tube coated with a dopamine layer, namely a dopamine modified carbon nano tube;
mixing a surfactant, an organic ligand, dopamine modified regenerated carbon fibers, dopamine modified carbon nanotubes and an organic solvent, adding the mixture into a metal salt solution, stirring and mixing for 1-2h, carrying out hydrothermal reaction in a reaction kettle, washing, centrifuging and drying after the reaction is finished, and carrying out high-temperature carbonization treatment on the obtained product at 500-900 ℃ in a protective gas atmosphere to obtain the carbon nanotube/regenerated carbon fiber composite material uniformly loaded with nano magnetic metal particles @ porous carbon;
carrying out vacuum filtration on the obtained product under the condition of a magnetic field to form a film, impregnating and backfilling the film with resin, and carrying out heat treatment to obtain a flexible regenerated recycled carbon fiber electromagnetic shielding composite material;
the regenerated carbon fiber is a short-cut regenerated carbon fiber prepared by high-temperature cracking of a carbon fiber composite material, or a short-cut regenerated carbon fiber prepared by cutting the regenerated carbon fiber prepared by high-temperature cracking of the carbon fiber composite material, the length of the short-cut regenerated carbon fiber is 3-8mm, and a metal salt solution adopted in the preparation of the carbon nanotube/regenerated carbon fiber composite material uniformly loaded with nano magnetic metal particles @ porous carbon is as follows: the nickel salt and/or cobalt salt are dissolved in organic solvent.
2. The preparation method of the flexible regenerated carbon fiber electromagnetic shielding composite material according to claim 1, wherein the regenerated carbon fiber is subjected to dopamine surface modification treatment, and the preparation method comprises the following specific steps:
(11) adding the Tris into ionic water for dissolving to obtain Tris solution, namely Tris solution, wherein the concentration range of the Tris solution is 10-20mmol/L, and dropwise adding acid solution to adjust the pH value to 8-8.5;
(12) preparing a dopamine solution by using the Tris solution prepared in the step (11), soaking the short-cut regenerated carbon fibers in the dopamine solution, and taking out the short-cut regenerated carbon fibers, wherein the concentration range of the dopamine solution is 2-4mg/mL, and the soaking time of the carbon fibers is 24-48 h;
(13) and (3) washing the reaction product obtained in the step (12) with deionized water for multiple times until the filtrate is colorless and clear, centrifuging and then placing in a vacuum oven for drying to obtain the dopamine modified regenerated carbon fiber, wherein the temperature of the oven is 50-100 ℃, and the drying time is 24-36 h.
3. The preparation method of the flexible regenerated carbon fiber electromagnetic shielding composite material according to claim 1, characterized in that the specific preparation method of the dopamine modified carbon nanotube comprises the following steps:
(21) adding the Tris into ionic water for dissolving to obtain Tris solution, namely Tris solution, wherein the concentration range of the Tris solution is 10-20mmol/L, and dropwise adding acid solution to adjust the pH value to 8-8.5;
(22) adding carbon nanotubes into a solvent, and uniformly dispersing by ultrasonic, wherein the carbon nanotubes are single-walled or multi-walled carbon nanotubes, and the solvent is deionized water or alcohol or a mixed solution of the deionized water and the alcohol;
(23) adding a certain mass of dopamine into the mixed solution obtained in the step (22), then adding the solution obtained in the step (21), and stirring for 4-8 hours to prepare a dopamine solution, wherein the mass concentration of the dopamine solution is 1-4 mg/mL;
(24) and (4) washing the product obtained in the step (23) with deionized water for multiple times until the filtrate is colorless and clear, centrifuging, and drying in a vacuum oven at the temperature of 50-100 ℃ for 24-36h to obtain the dopamine modified carbon nanotube.
4. The method for preparing the flexible regenerated carbon fiber electromagnetic shielding composite material as claimed in claim 1, wherein the molar ratio of nickel salt to cobalt salt in the metal salt solution is 1: 0. 2: 1. 1: 1. 1: 2 or 0: 1.
5. the method for preparing the flexible regenerated carbon fiber electromagnetic shielding composite material as claimed in claim 1, wherein the nickel salt and the cobalt salt are nitrate or acetate;
the organic solvent is one or a mixture of ethanol and N, N-dimethylformamide.
6. The method for preparing the flexible regenerated carbon fiber electromagnetic shielding composite material as claimed in claim 1, wherein the organic ligand is one of dimethylimidazole, terephthalic acid and trimesic acid.
7. The method for preparing the flexible regenerated carbon fiber electromagnetic shielding composite material as claimed in claim 1, wherein the hydrothermal reaction temperature is 100-150 ℃ and the hydrothermal reaction time is 20-40 h.
8. The method for preparing the flexible regenerated carbon fiber electromagnetic shielding composite material as claimed in claim 1, wherein the carbonization time is 2-4h, and the temperature rise rate is 5-10 ℃/min.
9. The preparation method of the flexible regenerated carbon fiber electromagnetic shielding composite material according to claim 1, wherein the vacuum filtration film forming process is carried out under a magnetic field, and the obtained magnetic chopped regenerated carbon fiber composite material is subjected to orientation treatment;
the resin adopted by the impregnation backfilling is thermoplastic polyurethane, polyimide or acrylonitrile-butadiene-styrene copolymer (ABS); the heat treatment temperature is 100-350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110849943.1A CN113444357B (en) | 2021-07-27 | 2021-07-27 | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110849943.1A CN113444357B (en) | 2021-07-27 | 2021-07-27 | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113444357A CN113444357A (en) | 2021-09-28 |
| CN113444357B true CN113444357B (en) | 2022-07-08 |
Family
ID=77817436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110849943.1A Active CN113444357B (en) | 2021-07-27 | 2021-07-27 | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444357B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114369955B (en) * | 2021-12-30 | 2023-04-25 | 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 fiber |
| CN114561805B (en) * | 2022-01-25 | 2023-04-18 | 中国人民解放军国防科技大学 | Flexible electromagnetic shielding material and preparation method thereof |
| CN114908610A (en) * | 2022-04-29 | 2022-08-16 | 上海交通大学 | Regenerated carbon fiber paper and preparation method thereof |
| CN115521578B (en) * | 2022-09-27 | 2024-01-26 | 合肥迈微新材料技术有限公司 | Preparation of double-solid waste composite high-strength high-resistivity insulating electromagnetic shielding and electromagnetic absorbing material |
| CN116355501A (en) * | 2023-02-28 | 2023-06-30 | 中国船舶集团有限公司第十二研究所 | Preparation method of carbon nano tube-chopped carbon fiber composite modified epoxy coating |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101470524B1 (en) * | 2009-06-30 | 2014-12-08 | 한화케미칼 주식회사 | Blending improvement carbon-composite having Carbon-nanotube and its continuous manufacturing method |
| CN106423154B (en) * | 2016-09-22 | 2018-10-30 | 华中科技大学 | A kind of three-dimension flexible electrode or three-dimension flexible catalyst and their preparation and application |
| CN107629461A (en) * | 2017-10-19 | 2018-01-26 | 北京大学 | A kind of efficient modification functionalization means for inactive surfaces |
| KR20190079025A (en) * | 2017-12-27 | 2019-07-05 | 울산과학기술원 | Dopamine assisted mechanically enhanced graphene oxide fiber and reduced graphene oxide fiber |
| CN108610628B (en) * | 2018-04-27 | 2020-05-22 | 华南理工大学 | Modified carbon fiber/nano aramid fiber composite material and preparation method thereof |
| CN109181228A (en) * | 2018-08-24 | 2019-01-11 | 天津大学 | A kind of preparation method of dopamine enveloped carbon nanometer tube modified carbon fiber reinforced resin based structures-damp composite material |
| CN110248530B (en) * | 2019-06-29 | 2021-11-23 | 华南理工大学 | Wearable breathable self-cleaning high electromagnetic shielding film and preparation method thereof |
| CN111116992B (en) * | 2019-12-27 | 2021-11-30 | 洛阳尖端装备技术有限公司 | Modified carbon fiber, preparation method and application |
| CN112441796B (en) * | 2020-12-07 | 2023-01-17 | 湖北工业大学 | Electromagnetic shielding cement-based composite material prepared by wet-grinding titanium slag and preparation method thereof |
| CN113024995B (en) * | 2021-02-04 | 2022-02-18 | 东华大学 | High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof |
-
2021
- 2021-07-27 CN CN202110849943.1A patent/CN113444357B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113444357A (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113444357B (en) | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material | |
| CN112195013B (en) | Method for synthesizing porous magnetic metal oxide/carbon composite wave-absorbing material | |
| CN109014245B (en) | Nitrogen-doped carbon-coated magnetic nanoparticle composite microsphere and preparation method thereof | |
| CN106866148A (en) | The SiC of SiC nanowire In-sltu reinforcementf/ SiC ceramic matrix composite material and preparation method thereof | |
| CN110938407A (en) | Hierarchical-structure hollow CNTs/Co/C fiber wave-absorbing material and preparation method thereof | |
| CN111116992B (en) | Modified carbon fiber, preparation method and application | |
| CN112225220B (en) | MXene/Ni composite material and preparation method and application thereof | |
| CN109252359B (en) | Preparation method of carbon nanotube modified carbon fiber reinforced resin-based electromagnetic shielding composite material for in-situ growth of solid carbon source | |
| CN110342531B (en) | Iron powder coated silicon dioxide material and preparation method thereof | |
| CN105524909B (en) | Chitosan magnetic micro-sphere, preparation method and application for enzyme immobilization | |
| CN108617154A (en) | A kind of porous carbon load nano nickel absorbing material and preparation method thereof | |
| CN102493204B (en) | Preparation method of hanging wave absorbing composite material | |
| CN113667159A (en) | Preparation method of cellulose-based electromagnetic shielding film of flexible regenerated carbon fiber and product thereof | |
| CN110282952A (en) | The composite material and preparation method for having electromagnetic shielding and shape-memory properties | |
| CN113329606B (en) | Magnetic metal/reduced graphene oxide aerogel composite wave absorbing agent and preparation method thereof | |
| CN114197201B (en) | Magnetic graphene oxide modified carbon fiber and preparation method and application thereof | |
| CN115212868A (en) | Nano metal particle loaded reduced graphene oxide aerogel and preparation method thereof | |
| CN114614272A (en) | MXene/Co/C composite wave-absorbing material derived from MOF and preparation method thereof | |
| CN104477872B (en) | Three-dimensional carbon nano material and preparation method and application thereof | |
| CN111943167A (en) | Cellulose carbon-based nano zero-valent iron material and preparation method thereof | |
| CN117377304B (en) | Co/carbon nano tube/foam carbon electromagnetic shielding composite material and preparation method thereof | |
| CN114345249B (en) | High-strength hollow composite microsphere with three-layer spherical shell structure and preparation method and application thereof | |
| CN117625129A (en) | Fiber/magnetic metal-carbon nano sheet composite material and preparation method thereof | |
| CN113015422B (en) | Cobalt-nickel alloy/reduced graphene oxide nanocomposite for shielding high-frequency electromagnetic waves, and preparation method and application thereof | |
| CN116161678A (en) | Preparation method of efficient wave-absorbing composite material CoFe@CNTs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |