CN107820382A - A kind of method for preparing ultralight electromagnetic shielding composite material - Google Patents
A kind of method for preparing ultralight electromagnetic shielding composite material Download PDFInfo
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- CN107820382A CN107820382A CN201710844397.6A CN201710844397A CN107820382A CN 107820382 A CN107820382 A CN 107820382A CN 201710844397 A CN201710844397 A CN 201710844397A CN 107820382 A CN107820382 A CN 107820382A
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- electromagnetic shielding
- paper
- carbon
- composite material
- polyaniline
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
A kind of method for preparing ultralight electromagnetic shielding composite material, specific steps include：The carbon fiber paper for being cleaned and dried processing is placed in electrochemistry three-electrode system, using electrochemical polymerization technology between the fiber surface and fiber and fiber of carbon fiber paper one layer of electrically conductive polyaniline web of aggregation deposition, build the multiple dimensioned carbon paper polyaniline structure body with complete conductive network, increase the interface adhesiveness between carbon fiber paper and resin matrix simultaneously, obtain a kind of mechanical strength height, lighting, the significant composite of electromagnetic shielding efficiency.
Description
Technical field
It is specially a kind of to utilize polyaniline-modified carbon fiber paper and tree the present invention relates to carbon-based electromagnetic shielding material field
The compound method for preparing electromagnetic shielding material of fat.
Background technology
Along with the rapid development of electronics industry, a large amount of electrical equipment and electronic equipment are widely used in industrial production and people's day
Often in life, the health of people is also endangered while bringing convenient.For example, PC and portable electronic
Widely using for device result in serious electromagnetic interference pollution, the electromagnetic interference (EMI) emissions of free space and ubiquitous radiation
Normal operation of the source all to health and electronic device causes serious harm, therefore, various electromagnetic shielding materials
Arise at the historic moment.So-called electromagnetic shielding, entity or non-physical housing exactly is made using conductive or magnetic conduction material, by electromagnetism
Interference is limited in certain scope, forms electromagnetic isolation.Popular saying is exactly (to have shielding specific function using shield
Material) stop or decay electromagnetic wave transmission.Preferable electromagnetic shielding material is in addition to the capability of electromagnetic shielding with superelevation, also
Should have the characteristics that super light weight, easy processing shaping, environmental suitability are strong.It is main but traditional electromagnetic shielding material is sheet metal
If steel plate, however, the shortcomings of steel plate own wt is big, cost is high, mobile difficult largely limits shielding material
Suitable application area.Therefore, studying new and effective electromagnetic shielding material turns into a kind of trend.The electromagnetic shielding researched and developed at this stage
Material mainly conductive electromagnetic screen coating, chemical plating stratotype electromagnetic shielding material, Multi-layer composite electromagnetic shielding material, this
A little shielding materials meet people to shielding electromagnetic waves demand to a certain extent, but due to high cost, high density etc. because
Element so that electromagnetic shielding material has new development trend.At present, the conducting polymer with ultralight, high electromagnetic efficiency is compound
Material turns into the first choice of electromagnetic shielding material, and wherein conductive filler is usually the carbon-based materials such as graphene, CNT.But mesh
The conducting polymer composite material of preceding research reduces the overall mechanics of composite while ultralight high electromagnetic efficiency is realized
Performance, it is difficult to meet actual demand.Therefore, seek a kind of to prepare high-strength, lighting, the conducting polymer of high electromagnetic shielding efficiency
The method of composite turns into a kind of development trend.
The content of the invention
The invention provides the Multifunctional electromagnetic shielding material system that a kind of high-strength light, low cost, performance are overlapped mutually
Preparation Method, mainly by using electropolymerization technology, thin layer low-density, Stability Analysis of Structures, good conductivity carbon fiber paper fiber
It polymerize one layer of electrically conductive polyaniline nano fiber net between surface and fiber, forms the multistage conductive network of carbon paper and polyaniline, structure
Porous carbon paper-polyaniline structure body is built out, it is then compound with resin matrix, it is modified, the multifunction electromagnetic screen of Composite
Cover material.
Technical scheme is completed by following steps：
First, carbon fiber paper is subjected to 0.5~3h of ultrasonic cleaning in organic solvent, carbon paper is then taken out into drying.It is described
Organic solvent for ethanol, acetone, ethyl acetate etc..
2nd, by the carbon paper being cleaned and dried dipping in the electrolytic solution, wherein electrolyte is aniline monomer and protonic acid doping
The mixed solution of agent composition, stands 1~6h, then using electropolymerization technology, carries out electric polymerization reaction by three-electrode system, instead
It is 5~35 DEG C to answer temperature, and the reaction time is 2~60min, and one layer of conducting polyaniline is polymerize between the fiber surface and fiber of carbon paper
Amine nanometer fiber net, obtain the composite conductive structure body of carbon paper and polyaniline.Then the carbon paper of acquisition-polyaniline structure body is entered
The processing of row cleaning-drying.
Described electrolyte is made up of aniline monomer and Bronsted acid, and wherein aniline monomer concentration is 0.2~2mol/L；Proton
Acid includes hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid etc., and proton acid concentration is 0.25~3mol/L.
Described three-electrode system：Working electrode is carbon paper, includes platinum filament, platinized platinum, carbon-point etc., reference electrode bag to electrode
Include saturation calomel, silver/silver chloride electrode etc..
3rd, it is the carbon paper of above-mentioned acquisition-polyaniline complex structure body and resin matrix is compound, so as to prepare multi-functional electricity
Magnetic shielding material.
Described resin matrix includes the heat curing-type trees such as epoxy resin, phenolic resin, acrylic resin, conductive epoxy resin
The thermoplastic resin such as fat, polyethylene, polyester.
This method realizes electrically conductive polyaniline web in carbon fiber paper in the case where keeping carbon paper itself superperformance
On homogeneous polymerization growth, obtain the good carbon paper of electric conductivity-polyaniline structure body so that the carbon paper as shield is being set
Complete continuous conductive path is formd in aliphatic radical body, while adds the Interface Adhesion performance of shield and resin matrix, is entered
And effectively prevent electromagnetic exposure and improve the mechanical property of material, obtain with thin layer lightweight, electromagnetic shielding efficiency is high,
The electromagnetic shielding material of easy processing shaping.
Brief description of the drawings
Fig. 1 is to polymerize the cyclic voltammogram that polyaniline obtains on carbon fiber paper using cyclic voltammetry
Fig. 2 is the scanning electron microscope (SEM) photograph of the carbon fiber paper coated by polyaniline fiber net
Embodiment
A kind of method for preparing ultralight electromagnetic shielding composite material provided by the invention is entered with reference to specific embodiment
Row describes in detail.
Embodiment 1：
Carbon paper is immersed in ethanol solution and is cleaned by ultrasonic 1h, is then taken out, processing is dried.Cleaning-drying is handled
Carbon paper dipping 1h in the electrolytic solution, the wherein concentration of aniline monomer is 0.2mol/L, and the concentration of hydrochloric acid is 1mol/L.Then exist
Under three-electrode system (working electrode is the carbon paper of dipping electrolyte, is carbon-point to electrode, reference electrode is saturated calomel electrode)
Using cyclic voltammetry, operating potential is -0.2~0.9V, sweep speed 50mV/S, gained cyclic voltammetry curve such as Fig. 1 institutes
Show, system reaction temperature is 25 DEG C, and the reaction time is 15 minutes, and electrically conductive polyaniline web is formed on carbon paper.By carbon paper-poly-
Aniline complex structure body cleans several times repeatedly in water and ethanol, drying process, as shown in Figure 2.
By the carbon paper of above-mentioned preparation-polyaniline complex structure body and epoxide resin vacuum dipping composite curing shaping, obtain
High-strength, lighting, carbon paper-polyaniline/epoxy resin composite material of high electromagnetic shielding efficiency, testing its tensile strength is about
411MPa, density are about 0.028g/cm3, conductance about 30.4S/cm, electromagnetic shielding efficiency 90.7dB.
Embodiment 2：
Carbon paper is immersed in acetone soln and is cleaned by ultrasonic 0.5h, taking-up is dried.Then processing will be cleaned and dried
Carbon paper impregnates 2h in the electrolytic solution, and the wherein concentration of aniline monomer is 0.5mol/L, and the concentration of sulfuric acid is 0.5mol/L.Then
(working electrode is the carbon paper of dipping electrolyte, is platinized platinum to electrode, and reference electrode is saturation calomel electricity under three-electrode system
Pole) galvanostatic method is used, specimen current density is 2mA/cm2, sweep speed 25mV/S, system reaction temperature is 20 DEG C, instead
It is 10 minutes between seasonable, the polymeric conductive polyaniline fiber net on carbon paper.Then by carbon paper-polyaniline complex structure body in water and
Rinsed repeatedly in ethanol several times, drying and processing.
The carbon paper of above-mentioned preparation-polyaniline complex structure body and phenolic resin vacuum impregnation composite curing are molded, obtained
High-strength, lighting, carbon paper-polyaniline/phenolic resin composite of high electromagnetic shielding efficiency, testing its tensile strength is
389MPa, density are about 0.021g/cm3, conductance about 29.6S/cm, electromagnetic shielding efficiency 78.3dB.
Embodiment 3：
Carbon paper is immersed in ethyl acetate solution and is cleaned by ultrasonic 1h, processing is dried in taking-up.Then will be cleaned and dried
The carbon paper of processing impregnates 1h in the electrolytic solution, and the wherein concentration of aniline monomer is 0.75mol/L, and the concentration of nitric acid is 1mol/L.
Then (working electrode is the carbon paper of dipping electrolyte, is carbon-point to electrode, and reference electrode is silver chlorate electricity under three-electrode system
Pole) potentiostatic method is used, sample current potential is 0.75V, and sweep speed 50mV/S, system reaction temperature is 28 DEG C, the reaction time
For 20 minutes, the polymeric conductive polyaniline fiber net on carbon paper.Then by carbon paper-polyaniline complex structure body in water and ethanol
In rinse repeatedly several times, drying and processing.
The carbon paper of above-mentioned preparation-polyaniline complex structure body and conductive epoxy resin vacuum impregnation composite curing are molded,
High-strength, lighting, carbon paper-polyaniline/epoxy resin composite material of high electromagnetic shielding efficiency are obtained, testing its tensile strength is
362MPa, density are about 0.037g/cm3, conductance about 39.8S/cm, electromagnetic shielding efficiency 98.3dB.
Claims (6)
- A kind of 1. method for preparing ultralight electromagnetic shielding composite material, it is characterised in that：It is fine in carbon using electrochemical polymerization technology It polymerize one layer of electrically conductive polyaniline nano fiber net between the fiber surface and fiber of dimension paper, builds the conductive network completely connected, And increase the Interface Adhesion performance between carbon paper and resin matrix, and then prepare high-strength, lighting and electromagnetic shielding efficiency surpasses High composite.
- 2. a kind of method for preparing ultralight electromagnetic shielding composite material described in claim 1, comprises the following steps：(1) carbon fiber paper is subjected to 0.5~3h of ultrasonic cleaning in organic solvent, carbon fiber paper is then taken out into drying.(2) by the carbon fiber paper being cleaned and dried dipping in the electrolytic solution, wherein electrolyte is aniline monomer and protonic acid doping The mixed solution of agent composition, stands 1~6h, then using electropolymerization technology, carries out electric polymerization reaction by three-electrode system, instead It is 5~35 DEG C to answer temperature, and the reaction time is 2~60min, and one layer of conduction is polymerize between the fiber surface and fiber of carbon fiber paper Polyaniline nano fiber net, obtain the conducting structures of carbon fiber paper and polyaniline.Then by carbon paper-polyaniline structure of acquisition Body carries out cleaning-drying processing.(3) it is the carbon paper of above-mentioned acquisition-polyaniline structure body and resin matrix is compound, so as to prepare high-efficiency electromagnetic shielding material Material.
- A kind of 3. method for preparing ultralight electromagnetic shielding composite material according to claim 2, it is characterised in that：Step (1) organic solvent is ethanol, acetone, ethyl acetate etc. in.
- A kind of 4. method for preparing ultralight electromagnetic shielding composite material according to claim 2, it is characterised in that：Step (2) electrolyte is made up of aniline monomer and Bronsted acid in, and wherein aniline monomer concentration is 0.2~2mol/L；Bronsted acid includes salt Acid, sulfuric acid, phosphoric acid, perchloric acid etc., proton acid concentration are 0.25~3mol/L.
- A kind of 5. method for preparing ultralight electromagnetic shielding composite material according to claim 2, it is characterised in that：Step (2) working electrode of three-electrode system is carbon fiber paper in, and platinum filament, platinized platinum, carbon-point etc. are included to electrode, and reference electrode includes full With calomel, silver/silver chloride electrode etc..
- A kind of 6. method for preparing ultralight electromagnetic shielding composite material according to claim 2, it is characterised in that：Step (3) resin matrix includes thermosetting resin and the poly- second such as epoxy resin, phenolic resin, acrylic resin, conductive epoxy resin in The thermoplastic resins such as alkene, polyester.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710844397.6A CN107820382A (en) | 2017-09-14 | 2017-09-14 | A kind of method for preparing ultralight electromagnetic shielding composite material |
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| CN201710844397.6A CN107820382A (en) | 2017-09-14 | 2017-09-14 | A kind of method for preparing ultralight electromagnetic shielding composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
| CN110337235A (en) * | 2019-07-23 | 2019-10-15 | 苏州盛达飞智能科技股份有限公司 | Carbon fiber electrically magnetic shielding material |
| CN111705545A (en) * | 2020-06-29 | 2020-09-25 | 连云港市工业投资集团有限公司 | Conductive polymer composite conductive paper and preparation method thereof |
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| US20070056769A1 (en) * | 2005-09-12 | 2007-03-15 | Severance Christopher L | Composite polymeric material for EMI shielding |
| CN101265339A (en) * | 2007-11-16 | 2008-09-17 | 兰州理工大学 | Method for preparing formable conducting polyaniline composite material |
| CN101613944A (en) * | 2009-07-10 | 2009-12-30 | 天津工业大学 | A kind of method that is used to improve shock resistance of resin-based carbon fiber composite material |
| CN104098834A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Conductive polymer composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
| CN109293918B (en) * | 2018-09-05 | 2021-05-11 | 东华大学 | Polyaniline nano-cluster and preparation method and device thereof |
| CN110337235A (en) * | 2019-07-23 | 2019-10-15 | 苏州盛达飞智能科技股份有限公司 | Carbon fiber electrically magnetic shielding material |
| CN111705545A (en) * | 2020-06-29 | 2020-09-25 | 连云港市工业投资集团有限公司 | Conductive polymer composite conductive paper and preparation method thereof |
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