CN103554530A - Electric conductive continuous fiber-reinforced fabric or prepreg and electric conductive treatment method - Google Patents
Electric conductive continuous fiber-reinforced fabric or prepreg and electric conductive treatment method Download PDFInfo
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- CN103554530A CN103554530A CN201310471829.5A CN201310471829A CN103554530A CN 103554530 A CN103554530 A CN 103554530A CN 201310471829 A CN201310471829 A CN 201310471829A CN 103554530 A CN103554530 A CN 103554530A
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Abstract
The invention belongs to the technical field of structural composite materials, and relates to an electric conductive continuous fiber-reinforced fabric or prepreg and an electric conductive treatment method. A continuous fiber-reinforced fabric and/or a prepreg thereof is used as a mechanical carrier and nano electric conductive components are directly loaded on the surface of the continuous fiber-reinforced fabric and/or the prepreg thereof, so that electric conductive functionalized continuous fiber-reinforced fabric or prepreg is obtained; then, a prefabricated structure including a sandwich structure is formed by spreading one layer or multi layers of the fabric or the prepreg mingled with unprocessed fabric or prepreg or all the fabric or the prepreg in different manners; and then, an electric conductive continuous fiber-reinforced structural composite material or sandwich composite material with adjustable electric conductivity and heat conductivity is prepared by a preparation process of a conventional composite material. The electric conductive and heat conductive composite material can fully keep structural mechanical performances of an original composite material.
Description
Technical field
The invention belongs to structural composite material technical field, relate to conduction continuous fibre reinforced fabric or prepreg and metallizing treatment process.
Background technology
The common electrical isolation of resin base structural composite material known in this field, continuous fibre strengthens, no matter these fortifying fibres are glass fibre, aramid fiber, superhigh molecular weight polyethylene fibers, ceramic fiber, basalt fibre, or the good carbon fiber of axial conduction etc.Therefore,, for antistatic, electromagnetic shielding, the object such as anti-lightning strike, this class formation matrix material must carry out conductive treatment conventionally.In like manner, the heat conductivility of this matrix material is general also lower.
The main method that improves this class formation conductivity of composite material has two kinds, one, to sneak into conductive component in the resin matrix of matrix material, as various metallicss etc. improve the electroconductibility of matrix material, more popular is in matrix resin, to add the conductive components such as carbon nanotube in recent years, as referenced patent US2009140098-A1 etc.; They are two years old, be in the bundle of continuous reinforcing fiber bundles, in interfascicular, layer, interlayer or at the thickness direction tramp m. fiber of matrix material, metal strip etc., be included in composite material surface and inner paving is covered wire netting (referenced patent WO2005032812-A2, US2005181203-A1) etc., or with hydridization electro-conductive materials such as carbon nanotube papers, replace metal strip, wire netting for weight reduction, as referenced patent CN102001448A, EP2289803-A2 and US2011049292-A1 etc.
The main drawback of filled conductive particle contact electricity transmission method is that electrical efficiency is low, and often a large amount of filled conductive particles are also difficult to obtain good conductive effect, also causes cost to increase; And for fear of reunion, sedimentation or the interface of conducting particles the technological problems such as incompatible, its technology of preparing and hybrid technique be also more complicated generally.The main drawback that mixes steel fiber, metal strip is that matrix material weightening finish and yardstick are not mated, and being starting material, the shortcoming that mixes carbon nanotube paper conductive method obtains difficulty, cost is high, and technique difficulty of preparation technology is large, its industry is amplified also more difficult, so this technology is at present only in the exploratory stage.
Summary of the invention
Object of the present invention: for the deficiency of above technology, the object of the invention is to propose a kind of conduction continuous fibre reinforced fabric or prepreg and metallizing treatment process.Adopt the medium modified traditional continuous fibre reinforced fabric of conductive nano and prepreg, make it there is more excellent electroconductibility, and then prepare the structural composite material of conductivity excellence, solve the deficiency of above-mentioned technology.
Object of the present invention is achieved through the following technical solutions:
Prepreg and the conducting medium of appendix on fabric or prepreg that this material is formed by continuous fibre reinforced fabric or continuous fibre reinforced fabric pre-soaked resin form; Conducting medium is nano silver wire, or one or more the mixture in nano silver wire and carbon nanotube, nano silver wire and Graphene, nano silver wire and conductive microfiber; The method of the prepreg that conducting medium appendix is formed to continuous fibre reinforced fabric or continuous fibre reinforced fabric pre-soaked resin is one of following three kinds of methods:
(1) conducting medium is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, dispersion liquid is painted on carrier, subsequently by appendix the fabric drying of conducting medium;
(2) conducting medium is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, then continuous fibre reinforced fabric or prepreg are immersed in dispersion liquid, take out subsequent drying;
(3) be directed to the continuous fibre reinforced fabric of conductive treatment, conducting medium is distributed in the solvent that does not dissolve continuous fibre reinforced fabric and do not destroy conducting medium and forms dispersion liquid, by dispersion liquid under negative pressure by continuous fibre reinforced fabric, subsequently by appendix the fabric drying of conducting medium.
Described continuous fibre reinforced fabric refers to glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, and its weaving manner is unidirectional, plain weave, twill or satin weave.
The continuous fibre reinforced fabric of described prepreg comprises glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, the weaving manner of fabric is unidirectional, plain weave, twill or satin weave, and the resin of preimpregnation is epoxy resin, unsaturated polyester, benzoxazine colophony, bimaleimide resin or polyimide resin.
The application of conduction continuous fibre reinforced fabric or prepreg, by above-mentioned conduction continuous fibre reinforced fabric or the single laying of prepreg or mix laying with continuous fibre reinforced fabric without conductive treatment or prepreg and form composite preform, conduction continuous fibre reinforced fabric in precast body or the number of plies of prepreg are for one or more layers or equal laying sum, and according to after the cure process curing molding of matrix material, make conduction or the improved composite product of heat conduction.
Described cure process is autoclave molding, Resin transfer molding moulding, mold pressing, vacuum aided or vacuum-bag process.
Advantage and disadvantage of the present invention is:
The present invention is usingd continuous fibre reinforced fabric and/or this reinforced fabric prepreg as mechanical carrier, on its surface, carry out the direct appendix of conductive nano component, simplified material preparation flow, greatly improved the utilization ratio of material therefor, prepare the continuous fibre reinforced fabric of high conductivity more and/or the intermediate state materials such as reinforced fabric prepreg of high conductivity more, only need the nano silver wire of load 1～2% can make the specific conductivity of fabric or prepreg increase approximately 100 times, and document (Ha M S, Kwon O Y, Choi H S.Improved Electrical Conductivity of CFRP by Conductive Silver Nano-particles Coating for Lightning Strike Protection[J] .) report that the colloid silver of load 10% just makes the specific conductivity of prepreg increase by four times, and the technology of preparing of these intermediate state materials is low-cost, can realizes easily technique and amplify.
By by one deck, or multilayer, or all adopt these intermediate state materials, paving is covered forming composite precast construction, according to the preparation technology of former conventional matrix material, prepare for different application, the structural composite material that the adjustable continuous fibre of electroconductibility strengthens, or sandwich composite, this conducing composite material keeps structure and the mechanical property of its original matrix material completely, its conductivity significantly improves, when the nano silver wire of unidirectional composite material plate load 1～2%, the outer specific conductivity of its face increases approximately 200 times, in face, 90 ° of direction specific conductivity increase approximately 330 times, in face, 0 ° of direction conductivity variations is little, and during document (H.S.Kim.Journal of Composite Materials2011,45 (10): 1109 – 1120) report matrix material load 2% Unidirectional nanotube, the outer specific conductivity of its face increases by 2.44 times, face internal conductance rate is unchanged.
Because preferred main ingredient of conducting electricity appendix material is nano silver wire, therefore the structural composite material of conductive treatment of the present invention has good heat conductivility concurrently simultaneously.
And aspect processing and forming technique, the composite material conductive treatment technology that the present invention proposes and the technology of preparing of former conventional structure matrix material are completely compatible.
Embodiment
Below by embodiment, design of the present invention and technology of preparing are described in further details.
The prepreg that the continuous fibre reinforced fabric of conductive treatment and prepreg are formed by continuous fibre reinforced fabric or continuous fibre reinforced fabric pre-soaked resin and the conducting medium being attached on fabric or prepreg form; Conducting medium is nano silver wire, or one or more the mixture in nano silver wire and carbon nanotube, nano silver wire and Graphene, nano silver wire and conductive microfiber.
Continuous fibre reinforced fabric refers to the fabric of glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, and its weaving manner can be unidirectional, plain weave, twill, satin weave.
The fabric that the continuous fibre reinforced fabric of prepreg comprises glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, the weaving manner of fabric is unidirectional, plain weave, twill, satin weave.The resin of preimpregnation is epoxy resin, unsaturated polyester, benzoxazine colophony, bimaleimide resin, polyimide resin.
One of by conducting medium appendix, to the method for continuous fibre reinforced fabric and prepreg, be following methods:
(1) conductive component is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, dispersion liquid is painted on carrier, subsequently by appendix the fabric drying of conducting medium;
(2) conductive component is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, then continuous fibre reinforced fabric or prepreg are immersed in this dispersion liquid, take out subsequent drying;
(3) be directed to the continuous fibre reinforced fabric of conductive treatment, conductive component is distributed in the solvent that does not dissolve continuous fibre reinforced fabric and do not destroy conducting medium and forms dispersion liquid, by dispersion liquid under negative pressure by continuous fibre reinforced fabric, subsequently by appendix the fabric drying of conducting medium.
By above-mentioned conduction continuous fibre reinforced fabric or the single laying of prepreg or mix laying with continuous fibre reinforced fabric without conductive treatment or prepreg and form composite preform, the continuous fibre reinforced fabric of the conductive treatment in precast body and the number of plies of prepreg are for one or more layers or equal laying sum, and according to after the cure process curing molding of matrix material, make the composite product with layer-selective conduction, heat conduction or monolithic conductive, heat conduction, or the sandwich composite product of panel selective conductivity, heat conduction.
Wherein the cure process of matrix material can be autoclave molding, Resin transfer molding moulding (RTM), mold pressing, vacuum aided or vacuum-bag process.Concrete operations are carried out according to the former condition of molding of matrix resin.
Embodiment 1:
The implementation process of technical solution of the present invention is as follows:
(1-1) nano silver wire is scattered in and in ethanol or Virahol or acetone or ethylene glycol or water, forms the dispersion liquid that concentration is 5mg/mL or 10mg/mL;
(1-2) by a carbon fibre fabric, carbon fiber T800,12K or CCF300,3K, being immersed in the nano silver wire content that above-mentioned steps (1-1) obtains is in the dispersion liquid of 5mg/mL or 10mg/mL, draws and proposes liquid level and dry or dry; Reverse dipping more once, according to appendix amount, require to determine dipping number of times, finally obtain the conductive carbon fibres dimensional fabric of even appendix nano silver wire.Repeat this step, obtain the conduction reinforced fabric material of multiple this intermediatenesses;
(1-3) the conduction intermediate state fabric above-mentioned (1-2) appendix being obtained, the order designing according to conventional matrix material laying and principle one by one lamination paving are covered, and obtain the carbon fibre fabric precast body of conduction;
(1-4) utilize resin transfer moulding (RTM) technique, by liquid-state epoxy resin 3266(Beijing Research Inst. of Aeronautic Material product) or liquid benzoxazine (BOZ) resin (the German Henkel product E psilon of company), according to the processing requirement of this resin RTM moulding, inject the conductive fabric precast body of above-mentioned (1-3) gained, and then be cured moulding by the technique of selected resin regulation, finally obtain the structural composite material goods of the carbon fibre fabric enhancing of nano silver wire surface appendix, this matrix material has higher electroconductibility, its heat conductivility is good simultaneously.Than the matrix material of appendix nano silver wire not, in the structural composite material face that the carbon fibre fabric of nano silver wire surface appendix strengthens, vertical fibers direction electroconductibility has improved 330 times, thickness direction electroconductibility has improved nearly 200 times, has effectively improved the conductivity of matrix material.
(1-5) if desired, the intermediate state electro-conductive material that step (1-2) can also be prepared only paving at one or positive and negative two outside surfaces of carbon fibre fabric precast body, but not the lamination one by one of the described this intermediate state material of whole employings of step (1-3) is prefabricated, then, according to step (1-4), precast body is carried out moulding and solidified equally, obtain the carbon fiber structural matrix material of upper layer conduction, this matrix material has excellent surface conduction character, but the use minimizing of conductive component, thereby cost is cheaper, the electromagnetic shielding and the lightning Protection that are suitable for matrix material,
(1-6) carbon fibre fabric of changing in this embodiment is that glasscloth, aramid fiber fabric, basalt fibre fabric or ceramic fabric are as silicon carbide fiber fabric, repeat above-mentioned step (1-1) to (1-5), prepare the structural composite material that glasscloth strengthens, kevlar fabric strengthens, basalt fibre fabric strengthens or silicon carbide fiber fabric strengthens that has conduction, heat conduction concurrently.
Embodiment 2:
The implementation process of technical solution of the present invention is as follows:
(2-1) nano silver wire is scattered in 2:1 (V:V) mixed solution of methyl alcohol or Virahol or acetone or alcohol and water or water and forms the dispersion liquid that concentration is 2mg/mL or 4mg/mL;
(2-2) by 3233 epoxy prepregs (Beijing Research Inst. of Aeronautic Material's product) or QY9611 epoxy prepreg (Beijing Aviation manufacturing engineering institute product) drawout, with nano silver wire dispersion liquid prepared by step (2-1), spray to equably one or positive and negative two surfaces, and require to determine spraying number of times according to appendix amount, obtain 3233 or QY9611 prepreg intermediate state material of the conduction of even appendix nano silver wire;
(2-3) the intermediate state conduction prepreg above-mentioned appendix being obtained, according to the laying design of former matrix material, carries out lay one by one, forms composite preform;
(2-4) curing process of stipulating by institute's epoxy prepreg that adopts, utilizes autoclave method or hot moulding method to be cured moulding, obtains the conduction of nano silver wire appendix, the structural composite material goods of heat conduction;
(2-5) the nano silver wire dispersion liquid in exchonge step (2-1) is carbon nano tube dispersion liquid, and adopting butanols or methyl alcohol or tetrahydrofuran (THF) is medium; Or the nano silver wire in (2-1) is replaced by nano silver wire, Graphene, the ternary of carbon nanotube in butanols or methyl alcohol or tetrahydrofuran (THF) medium dispersion liquid altogether, three's concentration is respectively: nano silver wire 4mg/mL, Graphene concentration is 1mg/mL, carbon nanotube concentration is 4mg/mL, and conducting medium total concn is 9mg/mL;
(2-6) by the carbon nano tube dispersion liquid of above-mentioned (2-5) step, or nano silver wire, Graphene, carbon nanometer pipe ternary dispersion liquid altogether, utilize the method for above-mentioned (2-2), the surface of same appendix to 3233 or QY9611 prepreg, obtain carbon nanotube, or nano silver wire, Graphene, carbon nanometer pipe ternary 3233 or the QY9611 conduction intermediate state material of appendix altogether;
(2-7) by above-mentioned (2-6) surperficial appendix carbon nano tube dispersion liquid, or nano silver wire, Graphene, carbon nanometer pipe ternary altogether 3233 or QY9611 prepreg intermediate state material of appendix spreads respectively to overlay on one of aramid paper honeycomb or upper and lower surfaces and forms panel, by the curing process of this epoxy prepreg and former cellular type core matrix material regulation thereof, utilize autoclave method or hot-press molding method to be cured moulding, obtain carbon nanotube appendix, or nano silver wire, Graphene, carbon nanometer pipe ternary is the cellular type core matrix material of appendix altogether, panel of this sandwich composite or upper and lower surfaces plate conduction.
Embodiment 3:
The implementation process of technical solution of the present invention is as follows:
(3-1) nano silver wire is scattered in to the dispersion liquid that forms 5mg/mL in ethanol, carboxy-modified carbon nanotube dispersed is formed to the dispersion liquid of 2mg/mL or 10mg/mL in water or in acetone or in DMF;
(3-2) by above-mentioned solid content, be the dispersion liquid of the carboxy-modified carbon nanotube (CNT) of 2mg/mL or 10mg/mL, utilize the method appendix make dispersion liquid pass through carrier under negative pressure to glasscloth on; After dry, then the glasscloth of this CNT appendix is immersed in the alcohol dispersion liquid that nano silver wire content is 5mg/mL, draw and propose liquid level and dry, obtain the electroconductive glass fibre fabric intermediate state material of the two appendix of nano silver wire and carbon nanotube;
(3-3) the electroconductive glass fibre fabric intermediate state material above-mentioned pair of appendix being obtained carries out laying one by one, obtains the glass fiber compound material precast body of conduction;
(3-4) adopt this precast body, the step (1-4) in repetition above-described embodiment 1 is to (1-5) or vacuum forming method, and curing molding obtains nano silver wire and the two appendix of carbon nanotube, height conduct electricity, the glass fiber compound material goods of heat conduction;
(3-5) the glass fibre intermediate state material of the two appendix in above-mentioned (3-2) surface is spread respectively overlay on one of aramid paper honeycomb or upper and lower surfaces and form panel, utilize RTM forming method or vacuum forming method, by 3266 or Epsilon liquid resin according to the forming requirements of this resin, suck, and then be cured by the technique of selected resin regulation, finally obtain the cellular type core composite product of the two appendix of nano silver wire and carbon nanotube, high conduction.
Embodiment 4:
The implementation process of technical solution of the present invention is as follows:
(4-1) nano silver wire, nickel plating carbon nano fiber are scattered in altogether in Virahol or water and form dispersion liquid, both concentration is respectively: nano silver wire 1mg/mL, and nickel plating carbon nano fiber 10mg/mL, conducting medium total concn is 11mg/mL; Again nano silver wire is scattered in to the dispersion liquid that forms 5mg/mL in Virahol;
(4-2) by the common dispersion liquid of above-mentioned nano silver wire and nickel plating carbon nano fiber, the method of utilizing dispersion liquid to spray, appendix is to the tow sides of aramid fiber fabric respectively, dry, again by the textile impregnation of this pre-appendix in the dispersion liquid of nano silver wire, obtain the conduction intermediate state material of two appendix;
(4-3) adopt this intermediate state material, step (1-3) in repetition above-described embodiment 1 is to (1-5) or vacuum forming method, and curing molding obtains nano silver wire and the two appendix of nickel plating carbon nano fiber, height conduct electricity, the aramid fiber reinforced composite goods of heat conduction;
(4-4) the aramid fiber intermediate state material of the two appendix in above-mentioned (4-2) surface is spread respectively overlay on one of Polymethacrylimide (PMI) foam materials or upper and lower surfaces and form panel, utilize RTM forming method or vacuum forming method, by 3266 or Epsilon liquid resin according to the forming requirements of this resin, suck, and then be cured by the technique of selected resin regulation, finally obtain the PMI foam sandwich composite product of the two appendix of nano silver wire and nickel plating carbon nano fiber, the high conduction in surface.
Claims (5)
1. conduction continuous fibre reinforced fabric or prepreg and a metallizing treatment process, is characterized in that: prepreg and the conducting medium of appendix on fabric or prepreg that this material is formed by continuous fibre reinforced fabric or continuous fibre reinforced fabric pre-soaked resin form; Conducting medium is nano silver wire, or one or more the mixture in nano silver wire and carbon nanotube, nano silver wire and Graphene, nano silver wire and conductive microfiber; The method of the prepreg that conducting medium appendix is formed to continuous fibre reinforced fabric or continuous fibre reinforced fabric pre-soaked resin is one of following three kinds of methods:
(1) conducting medium is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, strength of solution is 1～20mg/mL, dispersion liquid is painted on carrier, subsequently by appendix the fabric drying of conducting medium;
(2) conducting medium is distributed to do not destroy and dissolve continuous fibre reinforced fabric or prepreg and do not destroy in the solvent of conducting medium and forms dispersion liquid, strength of solution is 1～20mg/mL, again continuous fibre reinforced fabric or prepreg are immersed in dispersion liquid, take out subsequent drying;
(3) be directed to the continuous fibre reinforced fabric of conductive treatment, conducting medium is distributed in the solvent that does not dissolve continuous fibre reinforced fabric and do not destroy conducting medium and forms dispersion liquid, strength of solution is 1～20mg/mL, by dispersion liquid under negative pressure by continuous fibre reinforced fabric, subsequently by appendix the fabric drying of conducting medium.
2. conduction continuous fibre reinforced fabric according to claim 1 or prepreg and metallizing treatment process, it is characterized in that: described continuous fibre reinforced fabric refers to glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, its weaving manner is unidirectional, plain weave, twill or satin weave.
3. conduction continuous fibre reinforced fabric according to claim 1 or prepreg and metallizing treatment process, it is characterized in that: the continuous fibre reinforced fabric of described prepreg comprises glass fibre, aramid fiber, basalt fibre, carbon fiber, superhigh molecular weight polyethylene fibers or ceramic fiber, the weaving manner of fabric is unidirectional, plain weave, twill or satin weave, and the resin of preimpregnation is epoxy resin, unsaturated polyester, benzoxazine colophony, bimaleimide resin or polyimide resin.
4. conduction continuous fibre reinforced fabric according to claim 1 or prepreg and metallizing treatment process, it is characterized in that: described conduction continuous fibre reinforced fabric or the application of prepreg, by above-mentioned conduction continuous fibre reinforced fabric or the single laying of prepreg or mix laying with continuous fibre reinforced fabric without conductive treatment or prepreg and form composite preform, conduction continuous fibre reinforced fabric in precast body or the number of plies of prepreg are for one or more layers or equal laying sum, and according to after the cure process curing molding of matrix material, make conduction or the improved composite product of heat conduction.
5. conduction continuous fibre reinforced fabric according to claim 4 or prepreg and metallizing treatment process, is characterized in that: described cure process is autoclave molding, Resin transfer molding moulding, mold pressing, vacuum aided or vacuum-bag process.
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