CN104711857B - Multicomponent electromagnetic shielding material based on carbon fiber and preparation method - Google Patents
Multicomponent electromagnetic shielding material based on carbon fiber and preparation method Download PDFInfo
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Abstract
Multicomponent electromagnetic shielding material based on carbon fiber, relates to electromagnetic shielding material production technical field.First remove oil preparation and the impurity on carbon fibre fabric surface, then at carbon fibre fabric surface aggregate conduction high polymer, then conductive black coating is coated in outside conduction high polymer.The material feature formed is: at carbon fibre fabric body peripheral hardware polymeric conductive biopolymer layer, in conduction high polymer layer outer cladding conductive black coating.Material of the present invention integrates the high-mechanical property of carbon fibre fabric and the waterproof wearability of coating, achieve the high effectiveness of 0.02～2.0GHz, electromagnetic shielding effect is notable, shield effectiveness is high, can be used for the lining material of electromagnetic shielding protective clothing and light structure building materials and the fabric of outdoor tent.
Description
Technical field
The present invention relates to electromagnetic shielding material production technical field.
Background technology
Protection to the electromagnetic shielding of human body at present mainly uses the mode directly dressed, currently employed most Electromagnetically shielding fabrics is to use metallic fiber manufacture or the form with non-metallic fibers blending to obtain, there is also some electromagnetic shielding materials using carbon fiber, and carbon fiber enbrittles due to itself, the most mostly using the electromagnetic shielding material of carbon fiber is to be mixed into net with staple in bulk or be directly incorporated into high polymer and be mixed.Such as a kind of composite in patent documentation CN103450665A, nylon, alloy powder, LDPE g MAH and antioxidant are uniformly mixed according to a ratio, on the twin screw extruder after melt blending, directly melt are clamp-oned impregnation mold.The fibre bundle that surface treated is crossed under tension, is sufficiently impregnated with by melt in entering impregnation mold die cavity.Fibre bundle after dipping is pulled out in mould, and carries out pelletizing after cooling, it is thus achieved that the elongate in shape pellet of a length of 10 ± 0.2mm.The composite obtained has the specific function to high and low frequency electromagnetic wave shielding, is also equipped with superior mechanical property specific to long fiber reinforced plastics simultaneously.As barrier material, can use and there is wave absorbtion or the single or multiple lift sheet material high to reflection of electromagnetic wave rate, a kind of electromagnetic shielding fabric for carbon fiber in patent documentation CN102465459A, barrier fabric is become by regenerated celulose fibre or polyacrylonitrile yarn weaving, it is heated to 280 DEG C with the muffle electric furnace speed of 10 DEG C minutes pre-oxidize, it is incubated 2 hours, under inert gas shielding, continuation muffle electric furnace is heated to 1000 DEG C with the speed of 15 DEG C/min, it is incubated 3 hours, obtain the carbon fiber yarn gauze of phosphorus content 90%, continue to be heated to 2000～3000 DEG C, obtain the graphite fibre yarn net of phosphorus content more than 99%, with this net as base fabric, dry method jet spinning is utilized to make various non-woven fabrics or body of wall shielding material.The method can be good at shielding the harm of the many human bodies of electromagnetic wave, and spinning process is simple, and production efficiency is high, has preferable economic and social benefit.A kind of electromagnetic screen textile by making textile produce shield effectiveness at the fiber surface of non-metallic fibers textile covering metal conducting layer in patent documentation CN1587494, it is metal-coated copper, nickel on substrate fiber surface, forms copper, nickel composite metal conducting film.I.e. first use electroless copper on substrate fiber surfaces such as nylon, terylene, acrylon, then electronickelling, form copper nickel composite metal conducting film at substrate surface, prepare electromagnetic screen textile.The Electromagnetically shielding fabrics of the porose flexibility of patent documentation CN201890978U, is distributed hole doped with on the flexible electromagnetic shielding fabric of the surface covering metal of carbon fiber, and the size in cavity is the 1/5 ~ 1/10 of the electromagnetic wavelength of required protection.Distance between the central point of hole is 5mm ~ 50mm, hole be shaped as squarish or sub-circular, the size of hole is 0.2 ~ 2mm, and hole takes mock leno weave to weave, and shield effectiveness is maintained at about 70dB.
Paster method on composite sheet is used to prepare electromagnetic shielding or inhale wave plate material, the laminar way utilizing material different also reaches specific wave-absorbing effect, if patent documentation CN 101444979A is a kind of frequency selection surface wave-absorbing material and preparation method thereof, utilize Multilayer Absorbing Material Coating complex technique, i.e. using at middle lay " ten " the font aluminium foil of layer glass fiber to realize the preparation of wide-band and wave-absorbing coating, the wave number of effectively inhaling in 2 ~ 8GHz reaches 16dB.
Summary of the invention
The technical problem to be solved is to provide the electromagnetic shielding material of a kind of carbon fibre fabric, so that the suction ripple shield effectiveness of electromagnetic wave is improved.
The multicomponent electromagnetic shielding material based on carbon fiber of the present invention, including carbon fibre fabric body, at carbon fibre fabric body peripheral hardware polymeric conductive biopolymer layer, in conduction high polymer layer outer cladding conductive black coating.
Material of the present invention integrates the high-mechanical property of carbon fibre fabric and the waterproof wearability of coating, achieve the high effectiveness of 0.02 ~ 2.0GHz, electromagnetic shielding effect is notable, and shield effectiveness is high, can be used for the lining material of electromagnetic shielding protective clothing and light structure building materials and the fabric of outdoor tent.
The present invention is processed on the basis of carbon fibre fabric and has been improved, and remains the outstanding mechanical performance of carbon fibre fabric, improves the easy brittle failure performance of carbon fiber, it is critical that electromagnet shield effect is superior.
Conductive black coating layer thickness of the present invention is 1～3mm.This coating layer thickness of the present invention can guarantee to be coated with in the coating by carbon fiber completely while increasing the grammes per square metre of carbon fibre fabric not too much.
The present invention another object is that the preparation method proposing above material.
Preparation method of the present invention comprises the following steps:
1) oil preparation and the impurity on carbon fibre fabric surface are removed；
2) at carbon fibre fabric surface aggregate conduction high polymer；
3) conductive black coating is coated in outside conduction high polymer.
Present invention process step simply goes up, rationally, it is easy to industrialized mass production, production process environmental protection.
Further: in described step 1), by carbon fibre fabric successively after acetone and hydrogen nitrate dipping, then after being neutralized to neutrality with sodium hydrate aqueous solution, with water rinsing, drying.Carbon fibre fabric after acetone nitric acid treatment is acidity, with in alkali and can reduce because fabric is that ensuing reaction is caused unnecessary impact by acidity.
In step 1), first carbon fibre fabric is immersed in acetone 20～30 hours, clean with clear water, dry after taking-up, again carbon fibre fabric is put in aqueous solution of nitric acid, under the conditions of 80 DEG C after reaction, rinse carbon fibre fabric with water, then with sodium hydrate aqueous solution, carbon fibre fabric is neutralized process.Acetone treatment can fully remove the oil preparation that carbon fibre fabric surface adds in the course of processing enough for a long time, on the one hand the reaction temperature of 80 DEG C can add the speed of fast response, it is unlikely to the most again to arrive the boiling point of nitric acid, makes nitric acid decompose, produce harmful nitrogen dioxide.
Described step 2) in, dry after carbon fibre fabric is placed in dodecylbenzene sodium sulfonate solution dipping, then be placed in FeCl3Impregnating in aqueous solution, be 0 DEG C～5 DEG C of pyrrole monomer solution reactions then at temperature, question response cleans after terminating, then will be dried.Dodecylbenzene sodium sulfonate solution processes the efficiency that can improve oxidation reaction, FeCl3Aqueous solution is possible to prevent the volatilization of pyrrole monomer as the oxidation reaction under the oxidant of oxidation reaction, low temperature environment.
Described step 2) in, the concentration for the dodecylbenzene sodium sulfonate solution of impregnation of carbon fibers fabric is 0.02mol/L, makes the oxidation reaction in solution more thorough by emulsification；For impregnating FeCl3The concentration of aqueous solution is 0.13mol/L, the FeCl of excess3Oxidation reaction can be made more complete；Pyrrole monomer solution concentration for reaction is 0.5mol/L, it is ensured that pyrrole monomer can be reacted completely, does not cause waste.
To step 2) operation 4～6 times, dodecylbenzene sodium sulfonate solution impregnation will be placed in, dries, is placed in FeCl again by carbon fibre fabric3Aqueous solution impregnates, is that 0 DEG C～5 DEG C of pyrrole monomer solution reactions, cleaning, dry cycle process 4～6 times in temperature.Enough conduction high polymers can be polymerized through the carbon fibre fabric surface of repeatedly circular treatment, thus there is more preferable electromagnet shield effect.
In described step 3), after conductive black powder, silane resin acceptor kh-550 and aqueous adhesive force diphenylguanidine N-630 mix homogeneously, add aqueous polyurethane, be uniformly mixed formation coating；Coating is uniformly coated on the positive and negative two sides of the dried carbon fabric after upper step processes.Carbon fibre fabric through coating coating has possessed certain water-proof function, can avoid the phenomenon of the easy sanding of carbon fibre fabric caused due to the fragility of carbon fiber simultaneously, and can improve the stability of carbon fibre fabric, is difficult to decoherence.
The too low meeting of conductive black mass content causes the electric conductivity of coating poor, and capability of electromagnetic shielding is relatively low；And the too high meeting of mass content of conductive black makes conductive black powder can not be completely dispersed in polyurethane, make the situation that coating is cracking.Therefore, in currently preferred coating, conductive black powder accounts for the 15% of coating gross mass.
Accompanying drawing explanation
Fig. 1 is the structural representation of product of the present invention.
Fig. 2 is the electromagnetic shielding effectiveness graph of a relation with wave frequency of product of the present invention.
Detailed description of the invention
One, further describe the present invention with example, but be not limiting as present disclosure.
In embodiment, raw materials used polyacrylonitrile (PAN) base carbon fibre endless tow (200tex/3000F), conductive black powder body, pyrrole monomer, ferric chloride, dodecylbenzene sodium sulfonate, acetone, nitric acid and polyurethane resin are commercially available prod.
1, the oil preparation of fabric face and impurity are removed:
Sample prepares: the carbon fibre fabric of purchase is cut into 1000mm × 1000mm size, is first coated the carbon fibre fabric on clipping path with resin during cutting, to ensure that the carbon fiber samples obtained after cutting is not decoherenced.Drying 1h at 60 DEG C, resin obtains sample after drying.
Sample is immersed in acetone, static 1d, repeatedly rinse with clear water after taking-up, dry.Being put into by the sample crossed through acetone treatment in the nitric acid of 70% concentration, condensing reflux, control temperature, at 80 DEG C, reacts 5h.First it is rinsed with a large amount of water after taking out sample, finally uses 3% sodium hydroxide solution to rinse sample, until the solution PH after Chong Xiing detects in neutrality, by samples dried.
2, at specimen surface polymeric conductive high polymer:
Take the carbon cloth using upper step process to process put into the dodecylbenzene sodium sulfonate solution that concentration is 0.02mol/L impregnates 1h after take out nature and dry；The sample processed is put into the FeCl that concentration is 0.13mol/L again3Take out after aqueous solution impregnates 1h, the sample processed be impregnated in the pyrrole monomer solution of 0.5mol/L again, under conditions of the temperature of reaction system is 0 DEG C～5 DEG C, reacts 12h.After question response terminates, first with dehydrated alcohol, sample is rinsed, more repeatedly clean with clear water, until cleaning the solution clarification obtained, then sample is put in vacuum drying oven under the cryogenic conditions that temperature is 60 DEG C, to be dried 4h, after cooling, take out sample.
By the sample of acquirement again from the beginning of being placed in dodecylbenzene sodium sulfonate solution impregnation, through drying, being placed in FeCl again3Aqueous solution impregnates, is that 0 DEG C～5 DEG C of pyrrole monomer solution reactions, cleaning, dry cycle process 4～6 times in temperature.
The final sample obtaining the enough conduction high polymers of polymerization, uses for lower step.
3, coating conductive black coating:
Coating prepares: by soluble in water for conductive black powder, add silane resin acceptor kh-550 and aqueous adhesive force diphenylguanidine N-630, by ultrasonic oscillator supersound process 30min, make conductive black powder be dispersed in water, and be sufficiently mixed with auxiliary agent silane resin acceptor kh-550 and aqueous adhesive force diphenylguanidine N-630.Add the aqueous polyurethane of certain mass afterwards, use electric blender stirring 30min, form coating.
Above silane resin acceptor kh-550, aqueous adhesive force diphenylguanidine N-630 are auxiliary agent, can increase the cohesive force between coating and carbon fibre fabric.Aqueous polyurethane is used for coated with conductive hydrocarbon black powder.
Coating: use wool brush that coating is uniformly coated on the positive and negative two sides of the dried carbon fabric after acetone nitric acid pre-treatment and conduction high polymer surface oxidation polymerization process, obtain electromagnetic wave screen fabric.
Two, product structure feature:
The product made is placed in magnifier, it can be observed that the structure shown in Fig. 1.
Carbon fibre fabric body is weaved formed by warp-wise carbon fiber 1 and broadwise carbon fiber 2, has conduction high polymer layer 3, in the conductive black coating 4 that conduction high polymer layer 3 outer cladding thickness is 1～3mm at warp-wise carbon fiber 1 and the outer in-situ polymerization respectively of broadwise carbon fiber 2.
Three, compliance test result:
The sample bench of testboard is made up of electromagnetic wave transparent material glass, the center of signal emitters, sample and signal receiving pole three is positioned on same straight line from top to bottom, and makes the spacing between the spacing between signal emitters and sample, sample and signal receiving pole be 15mm.After starting to measure, after the electro-magnetic wave contacts that signal emitters is launched to specimen surface, a part is reflected and absorbed, and another part passes through sample, and the electromagnetic intensity through sample parts receives through signal receiving pole, then reads via spectrum analyzer.
Taking the mode of frequency sweep, measurement scope is 0.05 ~ 2.0GHz, a width of 0.05GHz of sweep spacing band.Testing according to the regulation of National Electrical industry military standard " measuring method of SJ20524 1995 Materials ' Shielding Effectiveness ", computational methods are as follows:
If using power unit to use dBm, then formula (2-1) can be write as
In formula, SE is the electromagnet shield effect of material, dBM；P1For sample bench is not placed sample Time-frequency Spectrum Analysis instrument reading, dBm；P2For sample bench is placed sample Time-frequency Spectrum Analysis instrument reading, dBm.
Obtain electromagnetic shielding effectiveness figure, as shown in Figure 2, for electromagnetic shielding effectiveness (EMSE, the electro-magnetic shielding efficiency) curve chart of multicomponent electromagnetic shielding material based on carbon fiber, in whole test frequency range, there is preferable shield effectiveness.
Claims (6)
1. the preparation method of multicomponent electromagnetic shielding material based on carbon fiber, described multicomponent electromagnetic shielding material based on carbon fiber includes carbon fibre fabric body, at carbon fibre fabric body peripheral hardware polymeric conductive biopolymer layer, in conduction high polymer layer outer cladding conductive black coating, it is characterised in that comprise the following steps:
1) oil preparation and the impurity on carbon fibre fabric surface are removed；
2) at carbon fibre fabric surface aggregate conduction high polymer；
3) conductive black coating is coated in outside conduction high polymer；
It is characterized in that in described step 1), first carbon fibre fabric is immersed in acetone 20～30 hours, clean with clear water, dry after taking-up, again carbon fibre fabric is put in aqueous solution of nitric acid, under the conditions of 80 DEG C after reaction, rinse carbon fibre fabric with water, then with sodium hydrate aqueous solution, carbon fibre fabric is neutralized process.
Preparation method the most according to claim 1, it is characterised in that described step 2) in, dry after carbon fibre fabric is placed in dodecylbenzene sodium sulfonate solution dipping, then be placed in FeCl3Impregnating in aqueous solution, be 0 DEG C～5 DEG C of pyrrole monomer solution reactions then at temperature, question response cleans after terminating, then will be dried.
Preparation method the most according to claim 2, it is characterised in that described step 2) in, the concentration for the dodecylbenzene sodium sulfonate solution of impregnation of carbon fibers fabric is 0.02mol/L；For impregnating FeCl3The concentration of aqueous solution is 0.13mol/L；Pyrrole monomer solution concentration for reaction is 0.5mol/L.
Preparation method the most according to claim 2, it is characterised in that described step 2) in, described carbon fibre fabric is placed in dodecylbenzene sodium sulfonate solution impregnation, dries, be placed in FeCl again3Aqueous solution impregnates, is that 0 DEG C～5 DEG C of pyrrole monomer solution reactions, cleaning, dry cycle process 4～6 times in temperature.
The most according to claim 1, preparation method, it is characterised in that in described step 3), after conductive black powder, silane resin acceptor kh-550 and aqueous adhesive force diphenylguanidine N-630 mix homogeneously, add aqueous polyurethane, be uniformly mixed formation coating；Coating is uniformly coated on the positive and negative two sides of the dried carbon fabric after upper step processes.
The most according to claim 5, preparation method, it is characterised in that in described coating, conductive black powder accounts for the 15% of coating gross mass.
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| CN105538815B (en) * | 2016-01-12 | 2017-09-29 | 襄阳精鑫电子设备制造有限公司 | Carbon fiber-based fabric preparation method with electromagnetic protection function |
| CN105500595B (en) * | 2016-01-15 | 2018-01-23 | 广东劲胜智能集团股份有限公司 | A kind of carbon fiber shell and its preparation method of surface coating |
| CN106507653A (en) * | 2016-09-26 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | Adjustable polymeric conductor films of a kind of capability of electromagnetic shielding and preparation method thereof |
| CN107012721B (en) * | 2017-03-31 | 2018-08-28 | 江南大学 | A kind of preparation of ultra high efficiency carbon fiber electrically magnetic screen paper |
| CN110219166B (en) * | 2019-06-20 | 2021-10-26 | 中原工学院 | Preparation method of acrylic fiber blended electromagnetic shielding fabric |
| CN110446408B (en) * | 2019-07-26 | 2024-03-19 | 中国电子科技集团公司第三十三研究所 | Tearing-resistant high-conductivity P-type composite rubber gasket and manufacturing method thereof |
| CN114000296B (en) * | 2021-11-20 | 2023-09-05 | 无锡腾华电缆材料科技有限公司 | Conductive water-blocking yarn production equipment |
| 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 |
| CN115160866A (en) * | 2022-05-11 | 2022-10-11 | 北京邮电大学 | Method for preparing surface modified electromagnetic shielding material by joule heat treatment |
| CN115353740B (en) * | 2022-08-24 | 2023-09-12 | 上海市同仁医院 | Polysiloxane material with electromagnetic shielding function and preparation method thereof |
| CN115652618B (en) * | 2022-10-30 | 2024-02-27 | 同济大学 | Carbon fiber and heat conduction interface material with wave absorbing function and preparation method thereof |
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| US4877646A (en) * | 1988-06-27 | 1989-10-31 | Milliken Research Corporation | Method for making electrically conductive textile materials |
| CN1111219C (en) * | 1995-02-27 | 2003-06-11 | 北京航空航天大学 | Electric heating, shielding, anti-static multifunctional conductive fabric and its preparing method |
| CN1233758C (en) * | 2002-10-17 | 2005-12-28 | 沈阳金纳新材料有限公司 | Conductive electromagnetic shielding paint and application thereof |
| CN103290685B (en) * | 2012-02-22 | 2015-02-04 | 北京服装学院 | Method for preparing high-conductivity conductive fiber and fabric, prepared conductive fiber and fabric and applications thereof |
| CN204551115U (en) * | 2015-03-06 | 2015-08-12 | 扬州市职业大学 | Based on the multicomponent electromagnetic shielding material of carbon fiber |
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