CN114685939A - Wave-absorbing carbon fiber prepreg, preparation method thereof and wave-absorbing carbon fiber reinforced plastic - Google Patents
Wave-absorbing carbon fiber prepreg, preparation method thereof and wave-absorbing carbon fiber reinforced plastic Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 98
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 98
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000004918 carbon fiber reinforced polymer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 108
- 239000011347 resin Substances 0.000 claims abstract description 92
- 229920005989 resin Polymers 0.000 claims abstract description 91
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011159 matrix material Substances 0.000 claims abstract description 64
- 239000011358 absorbing material Substances 0.000 claims abstract description 54
- 229960003638 dopamine Drugs 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 34
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
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- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 9
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004643 cyanate ester Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract description 5
- 229920001690 polydopamine Polymers 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000002313 adhesive film Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
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- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
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- 239000006185 dispersion Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- -1 dopamine modified nickel Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08K3/08—Metals
- C08K2003/0843—Cobalt
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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Abstract
The invention provides wave-absorbing carbon fiber prepreg, a preparation method thereof and wave-absorbing carbon fiber reinforced plastic. The wave-absorbing carbon fiber prepreg comprises a resin matrix and carbon fibers impregnated with the resin matrix, wherein the resin matrix comprises a resin component to be cured and a wave-absorbing material, and the wave-absorbing material is dopamine-modified magnetic wave-absorbing particles. The dopamine is used for carrying out surface modification on the magnetic wave-absorbing particles, and a polydopamine coating layer is formed on the surfaces of the magnetic wave-absorbing particles. Compared with the common magnetic wave-absorbing particles, the dopamine modified magnetic wave-absorbing particles have good dispersibility in prepreg and are not easy to agglomerate due to the existence of dopamine active groups. Therefore, the dopamine modified magnetic wave-absorbing particles can be fully dispersed in the prepreg, and the structural uniformity of the material is obviously improved. The uniformly distributed magnetic wave-absorbing particles can simultaneously improve the mechanical property and the carbon fiber electromagnetic property of the finally formed carbon fiber composite material.
Description
Technical Field
The invention relates to the technical field of composite wave-absorbing materials, in particular to wave-absorbing carbon fiber prepreg, a preparation method thereof and wave-absorbing carbon fiber reinforced plastic.
Background
The carbon fiber/resin matrix composite material is a new generation structural material with the characteristics of light weight, high strength and the like, and has good application in the fields of automobiles, aviation aerospace, industrial rail transit and the like. Particularly in the field of wave-absorbing materials, carbon fibers belong to carbon materials and are common dielectric loss wave-absorbing agents, but the carbon fibers have large dielectric constant and poor impedance matching property, and the electromagnetic parameter characteristics of the carbon fibers need to be improved through structural and surface modification, doping and other treatments.
At present, in most wave-absorbing materials, the wave-absorbing agent has small dimension and is easy to agglomerate, so that the wave-absorbing performance of the material is unstable, and the mechanical property of the composite material is reduced more easily due to the uneven dispersion of the wave-absorbing agent in resin, thereby influencing the practical application.
Disclosure of Invention
The invention mainly aims to provide a wave-absorbing carbon fiber prepreg, a preparation method thereof and wave-absorbing carbon fiber reinforced plastic, so as to solve the problem that wave-absorbing materials in the wave-absorbing carbon fiber prepreg are not uniformly dispersed in the prior art.
In order to achieve the purpose, according to one aspect of the invention, the wave-absorbing carbon fiber prepreg comprises a resin matrix and carbon fibers impregnated with the resin matrix, wherein the resin matrix comprises a resin component to be cured and a wave-absorbing material, and the wave-absorbing material is dopamine-modified magnetic wave-absorbing particles.
Further, the magnetic wave-absorbing particles are Fe3O4Particles, Ni particles, Co particles and CoFe2O4The particle size of any one or more of the particles is preferably 10-100 nm, and the particle size of the dopamine modified magnetic wave-absorbing particle is preferably 15-105 nm.
Furthermore, the weight content of the resin matrix in the wave-absorbing carbon fiber prepreg is 20-55%, preferably 30-55%, and the weight content of the wave-absorbing material in the resin matrix is preferably 3-5%.
Further, the resin matrix is one or more of an epoxy resin matrix, a bismaleimide resin matrix and a cyanate ester resin matrix, and preferably, the epoxy resin matrix is one or two of a Kunshan Yubo YPH-160 type hot-melt epoxy resin matrix and a Huibei new material R2300 type hot-melt epoxy resin matrix.
Further, the carbon fiber has an areal density of 150 to 250g/m2Preferably, the surface density of the wave-absorbing carbon fiber prepreg is 280-360 g/m2。
According to another aspect of the invention, a preparation method of any one of the wave-absorbing carbon fiber prepregs is provided, and the preparation method comprises the following steps: step S1, dispersing wave-absorbing materials in a molten resin matrix to form a mixture, wherein the wave-absorbing materials are dopamine-modified magnetic wave-absorbing particles; and step S2, coating the carbon fiber on the mixture to obtain the wave-absorbing carbon fiber prepreg.
Further, the step S1 includes: heating the resin matrix to form a molten resin matrix; stirring and mixing the wave-absorbing material and the molten resin matrix at the rotating speed of 40-100 rpm for 60-90 min to obtain a mixture.
Further, the preparation method also comprises a preparation process of the wave-absorbing material, and the preparation process of the wave-absorbing material comprises the following steps: mixing the magnetic wave-absorbing particles with dopamine/Tris-HCl buffer solution at room temperature to form mixed solution; carrying out ultrasonic treatment on the mixed solution for 30-60 min, and stirring for 24-36 h to obtain a modified system; and washing and drying the modified system to obtain the wave-absorbing material, wherein the ultrasonic power is 150-250W, the stirring speed is 600-1200 rpm, and the drying temperature is 80-100 ℃.
According to another aspect of the invention, the wave-absorbing carbon fiber reinforced plastic is prepared by curing any wave-absorbing carbon fiber prepreg.
Furthermore, the wave-absorbing carbon fiber reinforced plastic comprises one or more layers of superposed wave-absorbing carbon fiber prepregs which are subjected to hot-pressing curing.
By applying the technical scheme of the invention, dopamine is used for carrying out surface modification on the magnetic wave-absorbing particles, and a polydopamine coating layer is formed on the surfaces of the magnetic wave-absorbing particles. Compared with the common magnetic wave-absorbing particles, the dopamine modified magnetic wave-absorbing particles have good dispersibility in prepreg and are not easy to agglomerate due to the existence of dopamine active groups. Therefore, the dopamine modified magnetic wave-absorbing particles can be fully dispersed in the prepreg, and the structural uniformity of the material is obviously improved. The uniformly distributed magnetic wave-absorbing particles can improve the mechanical property of the finally formed carbon fiber composite material on one hand, and can further improve the electromagnetic property of the carbon fiber composite material on the other hand. In conclusion, the dopamine modified magnetic wave-absorbing particles are utilized, so that the problem that the wave-absorbing material in the wave-absorbing carbon fiber prepreg is easy to disperse and uneven in the existing problem is solved, and the structural stability and the wave-absorbing performance of the carbon fiber composite material are improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
According to the description of the background art of the application, the wave-absorbing material in the wave-absorbing carbon fiber prepreg in the prior art is easy to agglomerate, so that the problem of uneven dispersion is caused. In order to solve the problems, the application provides a wave-absorbing carbon fiber prepreg, a preparation method thereof and wave-absorbing carbon fiber reinforced plastic.
In a typical embodiment of the application, the wave-absorbing carbon fiber prepreg comprises a resin matrix and carbon fibers impregnated with the resin matrix, wherein the resin matrix comprises a resin component to be cured and a wave-absorbing material, and the wave-absorbing material is dopamine-modified magnetic wave-absorbing particles.
According to the method, the dopamine is used for carrying out surface modification on the magnetic wave-absorbing particles by utilizing the self-polymerization effect of the dopamine, and a poly-dopamine coating layer is formed on the surfaces of the magnetic wave-absorbing particles. Compared with the common magnetic wave-absorbing particles, the dopamine modified magnetic wave-absorbing particles have good dispersibility in prepreg and are not easy to agglomerate due to the existence of dopamine active groups. Therefore, the dopamine modified magnetic wave-absorbing particles can be fully dispersed in the prepreg, and the structural uniformity of the material is obviously improved. The uniformly distributed magnetic wave-absorbing particles can improve the mechanical property of the finally formed carbon fiber composite material on one hand, and can further improve the electromagnetic property of the carbon fiber composite material on the other hand. In conclusion, the dopamine-modified magnetic wave-absorbing particles are utilized, so that the problem that the wave-absorbing material in the wave-absorbing carbon fiber prepreg is easy to disperse and uneven in the existing problem is solved, and the structural stability and the wave-absorbing performance of the carbon fiber composite material are improved.
The magnetic wave-absorbing particles used in the application can be the magnetic wave-absorbing particles commonly used in the prior art and capable of improving the electromagnetic parameter characteristics of the carbon fibers, and in order to further improve the wave-absorbing performance of the carbon fibers, the magnetic wave-absorbing particles are preferably Fe3O4Particles, Ni particles, Co particles and CoFe2O4The particle size of the magnetic wave-absorbing particles is preferably 10-100 nm, and the particle size of the dopamine modified magnetic wave-absorbing particles is preferably 15-105 nm. When the particle size of the magnetic wave-absorbing particles is smaller than the above numerical range, although the wave-absorbing effect is relatively good, the cost is obviously increased, so that the magnetic wave-absorbing particles smaller than 10nm are not used in the actual production.
In some embodiments, the weight content of the resin matrix in the wave-absorbing carbon fiber prepreg is 20-55%, the resin matrix in the weight content range can further ensure sufficient distribution in the carbon fibers, so as to play a role in uniform reinforcement and improve the structural stability of the composite material, and is further preferably 30-55%, when the content of the resin matrix is higher than the range of 55%, the tensile and bending properties of a final finished product can be reduced due to the reduction of the content of the carbon fibers, and when the content is lower than 30%, on one hand, the wave-absorbing property of the final finished product can be reduced due to the reduction of the content of the wave-absorbing agent along with the reduction of the content of the resin matrix, and on the other hand, the shear strength of the final finished product can be reduced due to the reduction of the content of the resin matrix. Preferably, the weight content of the wave-absorbing material in the resin matrix is 3-5%. The wave-absorbing material in the weight content range can effectively improve the electromagnetic parameter characteristics of the carbon fiber and can be well dispersed in the resin matrix.
The resin matrix can be selected from resin materials commonly used as a carbon fiber composite resin matrix by persons skilled in the art, and in order to further improve the dispersibility of the dopamine modified magnetic wave-absorbing particles in the resin aggregate, the resin matrix is preferably one or more of an epoxy resin matrix, a bismaleimide resin matrix and a cyanate ester resin matrix, and the resin matrix is preferably one or two of an YPH-160 type hot-melt epoxy resin matrix and an R2300 type hot-melt epoxy resin matrix. The epoxy group of the epoxy resin matrix and the amino group of the dopamine on the surface of the magnetic wave-absorbing particles are selected to form an amide group, so that the dispersibility of the magnetic wave-absorbing particles can be further improved.
In order to further reduce the overall quality of the material and enable the material to adapt to more application scenes, the surface density of the carbon fiber is preferably 150-250 g/m2Preferably, the surface density of the wave-absorbing carbon fiber prepreg is 280-360 g/m2。
In another exemplary embodiment of the present application, there is provided a preparation method of a wave-absorbing carbon fiber prepreg, including: step S1, dispersing wave-absorbing materials in a molten resin matrix to form a mixture, wherein the wave-absorbing materials are dopamine-modified magnetic wave-absorbing particles; and step S2, coating the carbon fiber on the mixture to obtain the wave-absorbing carbon fiber prepreg.
The preparation method comprises the step of dispersing the dopamine modified magnetic wave-absorbing particles in a molten resin matrix to ensure that the particles can be fully dispersed in the resin matrix. The dopamine modified magnetic wave-absorbing particles have a polydopamine coating layer on the surface, so that compared with common magnetic wave-absorbing particles, the dopamine modified magnetic wave-absorbing particles have good dispersibility in prepreg, and the uniformity of the material is further ensured. The uniformly distributed magnetic wave-absorbing particles can improve the mechanical property of the finally formed carbon fiber composite material on one hand, and can further improve the electromagnetic property of the carbon fiber composite material on the other hand. In conclusion, by the preparation method, the problem that the wave absorbing material in the wave absorbing carbon fiber prepreg is easy to disperse and uneven in the existing problem is solved, and the structural stability and the wave absorbing performance of the carbon fiber composite material are improved.
In one embodiment, the step S1 includes: heating the resin matrix to form a molten resin matrix; and stirring and mixing the wave-absorbing material and the molten resin matrix at the rotating speed of 40-100 rpm for 60-90 min to obtain a mixture. By the method, the resin matrix is heated to be in a liquid state, and then the wave-absorbing material is added under the condition of stirring, so that the wave-absorbing material is fully and uniformly dispersed, and the uniformity of the internal structure of the composite material is further improved.
The dopamine modified magnetic wave-absorbing particles can be made of the existing commercialized materials in the prior art, and can also be selected by the technical personnel in the field in the common dopamine modification method in the prior art. In order to obtain the wave-absorbing material with proper particle size and excellent magnetic property and be more beneficial to preparing the wave-absorbing carbon fiber prepreg, the preparation method preferably further comprises the preparation process of the wave-absorbing material, and the preparation process of the wave-absorbing material comprises the following steps: mixing the magnetic wave-absorbing particles with dopamine/Tris-HCl buffer solution at room temperature to form mixed solution; carrying out ultrasonic treatment on the mixed solution for 30-60 min, and stirring for 24-36 h to obtain a modified system; and washing and drying the modified system to obtain the wave-absorbing material, wherein the ultrasonic power is 150-250W, the stirring speed is 600-1200 rpm, and the drying temperature is 80-100 ℃. By the processing method, the self-polymerization of dopamine can be utilized to carry out surface modification on as many wave-absorbing particles as possible at one time, and the particle size of the formed wave-absorbing material can be effectively controlled, so that the wave-absorbing material which can be fully dispersed in a resin matrix and has excellent magnetic property can be obtained.
In another exemplary embodiment of the present application, a wave-absorbing carbon fiber reinforced plastic is provided, and the wave-absorbing carbon fiber reinforced plastic is formed by curing any one of the wave-absorbing carbon fiber prepregs. The dopamine modified magnetic wave-absorbing particles are used as the wave-absorbing material, so that the wave-absorbing material in the wave-absorbing carbon fiber reinforced plastic is fully dispersed. The existence of the magnetic wave-absorbing particles can effectively improve the problem of poor impedance matching of the carbon fiber composite material and improve the wave-absorbing performance of the composite material; on the other hand, the particles can concentrate stress around the particles in deformation to cause the yield of the surrounding resin matrix, thereby absorbing a large amount of deformation work, hindering and passivating the expansion of silver grains in the resin, playing a role in preventing destructive cracking and improving the mechanical property of the composite material. In conclusion, by utilizing the dopamine modified magnetic wave-absorbing particles, the wave-absorbing material is easy to disperse unevenly in the resin matrix, and the structural stability and the wave-absorbing performance of the wave-absorbing carbon fiber reinforced plastic are improved.
Therefore, the wave-absorbing carbon fiber reinforced plastic has excellent mechanical properties and further has excellent wave-absorbing properties, so that the application performance of the wave-absorbing carbon fiber reinforced plastic is remarkably improved.
In order to better control the weight ratio of the resin substrate, the content of the wave-absorbing material and the thickness and weight of the wave-absorbing carbon fiber reinforced plastic, so that the plastic composite material can be suitable for more application scenes, the wave-absorbing carbon fiber reinforced plastic is preferably prepared by hot-pressing and curing one or more layers of superposed wave-absorbing carbon fiber prepregs. The intensity of the wave-absorbing carbon fiber reinforced plastic can be adjusted by adjusting the hot-pressing pressure according to the application requirement by a person skilled in the art.
The following examples and comparative examples are provided to further illustrate the advantageous effects of the present application.
Example 1
(1) Mixing ferroferric oxide nano particles (Fe)3O4Particle size of 15-30 nm) at room temperature to DA concentration ofPreparing a mixed solution with the concentration of 1mg/mL in Tris-HCl buffer solution with the concentration of 2mg/mL and the pH value of 8, carrying out ultrasonic treatment at 250W for 30min, then stirring the mixed solution for 24h at room temperature (the stirring speed is 1200rpm), finally carrying out centrifugal washing by deionized water and drying at the temperature of 80 ℃ to prepare the baamine modified ferroferric oxide (DA-Fe)3O4The particle size is 20-35 nm, and the material is used as a wave-absorbing material);
(2) baking YPH-160 hot-melt epoxy resin in an oven at 80 deg.C for 30min, adding into a resin mixer, and adding DA-Fe3O4Adding 5% of the above components, mixing at 100rpm for 60min, taking out, and storing in a refrigerator, wherein the sample is YPH-Fe3O4；
(3) YPH-Fe was first introduced3O4The resin was taken out of the freezer and placed in an oven at 70 deg.C/30 min, after which YPH-Fe was put in3O4Pouring the resin into a coating device, wherein the roller rotating speed is 3m/min, and the gram weight is 120g/m2YPH-Fe of3O4Resin adhesive film, finally impregnating the adhesive film and the carbon fiber 3k plain fabric by using prepreg coating equipment to prepare the wave-absorbing carbon fiber prepreg (the prepreg areal density is 320 g/m)2The areal density of the carbon fiber 3k plain weave fabric was 185.6g, YPH-Fe3O442% by weight), the sample was labeled YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Example 2
(1) Adding nickel nanoparticles (Ni, the particle size of which is 15-30 nm) into Tris-HCl buffer solution with the concentration of 2mg/ml DA and the pH value of 8 at room temperature, preparing mixed solution with the concentration of 1mg/ml, carrying out ultrasonic treatment at 250W for 30min, stirring the mixed solution at room temperature for 24h, finally carrying out centrifugal washing by deionized water and drying at 80 ℃ to prepare dopamine modified nickel particles (DA-Ni, the particle size of which is 20-35, and used as a wave-absorbing material);
(2) baking YPH-160 type hot-melt epoxy resin in an oven at 80 ℃ for 30min, adding the epoxy resin into a resin mixer, adding DA-Ni according to the content of 5%, mixing the materials at the stirring speed of 100rpm for 60min, taking out the mixture, and placing the mixture in a cold storage for later use, wherein a sample is marked as YPH-Ni;
(3) firstly, taking out YPH-Ni resin from a refrigeration house, putting the YPH-Ni resin in an oven at 70 ℃/30min, then pouring the YPH-Ni resin into coating equipment, and making the weight of a roller at 3m/min2Finally, impregnating the YPH-Ni resin adhesive film and the carbon fiber 3k plain fabric by using prepreg coating equipment to prepare the wave-absorbing carbon fiber prepreg (the prepreg areal density is 320 g/m)2The areal density of the carbon fiber 3k scrim was 185.6g, YPH-Ni content 42%) and the sample was designated YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing the YPH-CF laminated board at the curing temperature of 120 ℃/4h and under the pressure of 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Example 3
(1) Adding cobalt nanoparticles (Co, the particle size of which is 15-30 nm) into Tris-HCl buffer solution with the concentration of 2mg/ml DA and the pH of 8 at room temperature, carrying out ultrasonic treatment for 30min at 250W, stirring the mixed solution at room temperature for 24h, finally, centrifugally washing by deionized water and drying at 80 ℃ to prepare dopamine-modified cobalt particles (DA-Co, the particle size of which is 20-35 nm, which are used as wave-absorbing materials);
(2) baking YPH-160 type hot-melt epoxy resin in an oven at 80 ℃ for 30min, adding the epoxy resin into a resin mixer, adding DA-Co according to the content of 5%, mixing the materials at the stirring speed of 100rpm for 60min, taking out the mixture and placing the mixture in a cold storage for later use, wherein a sample is marked as YPH-Co;
(3) firstly, taking out YPH-Co resin from a refrigeration house, putting the YPH-Co resin in an oven at 70 ℃/30min, then pouring the YPH-Co resin into coating equipment, and making the weight of a roller at 3m/min2Finally, impregnating the adhesive film and the carbon fiber 3k plain fabric by using prepreg coating equipment to prepare the wave-absorbing carbon fiber prepreg (the prepreg areal density is 320 g/m)2The areal density of the carbon fiber 3k plain weave fabric is 185.6g, the YPH-Co content is 42%) and the sample is marked as YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Example 4
(1) Mixing nanometer cobalt ferrite particles (CoFe)2O4Particle size of 15-30 nm) is added into Tris-HCl buffer solution with the concentration of 2mg/ml DA and the pH of 8 at room temperature to prepare mixed solution with the concentration of 1mg/ml, ultrasonic treatment is carried out for 30min at 250W, then the mixed solution is stirred for 24h at room temperature, finally the mixed solution is centrifugally washed by deionized water and dried at 80 ℃, and the dopamine modified nano cobalt ferrite particle (DA-CoFe) is prepared2O4The particle size is 20-35 nm, and the material is used as a wave-absorbing material);
(2) baking YPH-160 hot-melt epoxy resin in an oven at 80 ℃ for 30min, adding the baked epoxy resin into a resin mixer, and adding DA-CoFe2O4Adding 5% of the above components, mixing at 100rpm stirring speed for 60min, standing for 60min, taking out, placing in a cold storage, and marking the sample as YPH-CoFe2O4；
(3) Firstly, YPH-CoFe2O4 resin is taken out of a refrigeration house and put in an oven at 70 ℃/30min, then YPH-CoFe2O4 resin is poured into coating equipment, the rotating speed of a roller is 3m/min, a YPH-CoFe2O4 resin adhesive film with the gram weight of 120g/m2 is manufactured, and finally, the adhesive film and a carbon fiber 3k plain weave fabric are impregnated by utilizing prepreg coating equipment to prepare the wave-absorbing carbon fiber prepreg (the surface density of the prepreg is 320 g/m)2The carbon fiber 3k plain weave fabric had an areal density of 185.6g, YPH-CoFe2O4 wt% 42%), and the sample was designated YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Example 5
(1) Mixing ferroferric oxide nano particles (Fe)3O4Particle size of 15-30 nm) is added into Tris-HCl buffer solution with the concentration of 2mg/mL DA and the pH of 8 at room temperature to prepare mixed solution with the concentration of 1mg/mL, ultrasonic treatment is carried out for 30min at 250W, then the mixed solution is stirred for 24h at room temperature, finally the mixed solution is centrifugally washed by deionized water and dried at 80 ℃, and the dopamine modified tetraoxide is preparedFerroferric oxide (DA-Fe)3O4The particle size is 20-35 nm, and the material is used as a wave-absorbing material);
(2) baking R2300 type hot-melt epoxy resin in an oven at 80 ℃ for 30min, adding into a resin mixer, and adding DA-Fe3O4Adding 5% of the above components, mixing at 100rpm for 60min, taking out, and placing in a refrigerator for use, wherein the sample is marked as R-Fe3O4；
(3) Firstly taking out R-Fe3O4 resin from a refrigeration house, putting the resin in an oven at 70 ℃/30min, then pouring the R-Fe3O4 resin into coating equipment, rotating the roller at 3m/min to prepare an R-Fe3O4 resin adhesive film with the gram weight of 120g/m2, and finally impregnating the adhesive film and a carbon fiber 3k plain fabric by utilizing the prepreg coating equipment to prepare the wave-absorbing carbon fiber prepreg (the surface density of the prepreg is 320 g/m)2The areal density of the carbon fiber 3k scrim was 185.6g, R-Fe3O4 wt% 42%), and the sample was labeled YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Example 6
The difference from the embodiment 1 is that (1) the particle diameter of the ferroferric oxide nano particles is 10-25 nm, and DA-Fe3O4The particle size is 15-30 nm.
Example 7
The difference from the embodiment 1 is that (1) the particle diameter of the ferroferric oxide nano particles is 85-100 nm, and DA-Fe3O4The particle size is 90-105 nm.
Example 8
The difference from the embodiment 1 is that (1) the particle diameter of the ferroferric oxide nano particles is 120-135 nm, and DA-Fe3O4The particle size is 125-140 nm.
Example 9
The difference from the embodiment 1 is that (1) the particle diameter of the ferroferric oxide nano particles is 1-10 nm, and DA-Fe3O4The particle size is 5-10 nm.
Example 10
The difference from example 1 is that the prepreg areal density after curing in (3) is 360g/m2The area density of the carbon fiber 3k plain weave fabric is 162g/m2，YPH-Fe3O4The weight content was 55%.
Example 11
The difference from example 1 is that the prepreg areal density after curing in (3) is 280g/m2The surface density of the carbon fiber 3k plain weave fabric is 196g/m2，YPH-Fe3O4The weight content is 30%.
Example 12
The difference from example 1 is that the prepreg areal density after curing in (3) is 280g/m2The surface density of the carbon fiber 3k plain weave fabric is 224g/m2，YPH-Fe3O4The weight content is 20%.
Example 13
The difference from example 1 is that the prepreg areal density after curing in (3) is 375g/m2The surface density of the carbon fiber 3k plain weave fabric is 150g/m2，YPH-Fe3O4The weight content is 60%.
Example 14
The difference from example 1 is that DA-Fe in (2)3O4The content of (B) is 3%.
Example 15
The difference from example 1 is that DA-Fe in (2)3O4The content of (B) is 1%.
Example 16
The difference from example 1 is that DA-Fe in (2)3O4The content of (B) is 8%.
Example 17
The difference from example 1 is that YPH-160 type hot-melt epoxy resin was changed to Zhongweibei type 7180 type hot-melt cyanate ester resin in (2).
Example 18
The difference from example 1 is that YPH-160 type hot-melt epoxy resin was changed to Zhongwei Beihua 8201 type hot-melt bismaleimide resin in (2).
Example 19
The difference from the embodiment 1 is that in (2), YPH-160 type hot-melt epoxy resin is replaced by China comet cypress new material R2300 type hot-melt epoxy resin.
Example 20
The difference from example 1 is that the prepreg areal density after curing in (3) is 357g/m2The surface density of the carbon fiber 3k plain weave fabric is 250g/m2，YPH-Fe3O4The weight content is 30%.
Example 21
The difference from example 1 is that in (2) the material was mixed for 90min at a stirring speed of 40 rpm.
Example 22
The difference from example 1 is that in (1), the power of ultrasonic wave is 150W, the time is 60min, the stirring time is 36h, the stirring speed is 600rpm, and the drying temperature is 100 ℃.
Comparative example 1
(1) Firstly, taking out YPH-160 resin from a refrigeration house, putting the YPH-160 resin in an oven at 70 ℃/30min, then pouring the YPH-160 resin into coating equipment, rotating the roller at the speed of 3m/min to prepare a YPH-160 resin adhesive film with the gram weight of 120g/m2, and finally, impregnating the adhesive film and a carbon fiber 3k plain fabric by utilizing the prepreg coating equipment to prepare a wave-absorbing carbon fiber prepreg (the prepreg has the surface density of 320g/m2, the thickness of 0.25mm and the YPH-160 weight content of 42%) with a sample marked as YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Comparative example 2
(1) Baking YPH-160 hot-melt epoxy resin in an oven at 80 ℃ for 30min, adding the baked epoxy resin into a resin mixer, and adding Fe3O4Adding 5% of particles (with the particle diameter of 15-30 as a wave-absorbing material), mixing at a stirring speed of 1200rpm for 60min to obtain a wave-absorbing carbon fiber prepreg, taking out and placing in a refrigeration house for later use, wherein the sample is marked as YPH2-Fe3O4；
(2) Firstly, taking the YPH-Fe3O4 resin out of a refrigeration house andpouring YPH-Fe3O4 resin into a coating device at a roller rotation speed of 3m/min at 70 ℃/30min in an oven, preparing a YPH-Fe3O4 resin adhesive film with a gram weight of 120g/m2, and finally impregnating the adhesive film and a carbon fiber 3k plain fabric by using a prepreg coating device to prepare the wave-absorbing carbon fiber prepreg (the prepreg surface density is 320g/m2, the thickness is 0.25mm, and YPH-Fe is3O442% by weight), the sample was labeled YPH-CF;
(4) and (3) paving and pasting the YPH-CF laminated board by using an autoclave molding process, and then curing, wherein the curing temperature of the composite material is 120 ℃/4h, and the pressure is 0.6 MPa. And curing to obtain the wave-absorbing carbon fiber reinforced plastic.
Wave-absorbing performance and mechanical property test
The mechanical property and the wave-absorbing property of the wave-absorbing carbon fiber reinforced plastic prepared by the embodiment are tested.
Mechanical Property test
And (3) testing tensile property: electronic universal tester, model UTM5105 (shenzhen mitsui crossbar technologies ltd), the test method is referenced to ASTM standard: d3039-07.
And (3) testing the bending strength: electronic universal tester, model UTM5105 (shenzhen mitsui crossbar technologies ltd), the test method is referenced to ASTM standard: d7264-07.
And (3) testing the shear strength performance: electronic universal tester, model UTM5105 (shenzhen mitsubishi longitudinal and transverse technologies ltd), the test method is referred to ASTM standard: d4255-01.
According to the mechanical property test requirements, preparing the wave-absorbing carbon fiber reinforced plastics with the thicknesses corresponding to the embodiments and the comparative examples.
Test of wave-absorbing Property
The wave-absorbing carbon fiber reinforced plastics of the embodiments and the comparative examples are processed into a ring with the inner diameter of 3.04mm, the outer diameter of 7.0mm and the thickness of 2-3 mm, and an electromagnetic parameter test is carried out on the ring at 8.2-12.4GHz by adopting a coaxial line method and a vector network analyzer with the model of N5244A of Agilent company in America.
The test results are shown in table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the method, the dopamine is used for carrying out surface modification on the magnetic wave-absorbing particles by utilizing the self-polymerization effect of the dopamine, and a poly-dopamine coating layer is formed on the surfaces of the magnetic wave-absorbing particles. Compared with the common magnetic wave-absorbing particles, the dopamine modified magnetic wave-absorbing particles have good dispersibility in prepreg and are not easy to agglomerate due to the existence of dopamine active groups. Therefore, the dopamine modified magnetic wave-absorbing particles can be fully dispersed in the prepreg, and the structural uniformity of the material is obviously improved. The uniformly distributed magnetic wave-absorbing particles can improve the mechanical property of the finally formed carbon fiber composite material on one hand, and can further improve the electromagnetic property of the carbon fiber composite material on the other hand. In conclusion, the dopamine-modified magnetic wave-absorbing particles are utilized, so that the problem that the wave-absorbing material in the wave-absorbing carbon fiber prepreg is easy to disperse and uneven in the existing problem is solved, and the structural stability and the wave-absorbing performance of the carbon fiber composite material are improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The wave-absorbing carbon fiber prepreg is characterized in that the resin matrix comprises a resin component to be cured and a wave-absorbing material, and the wave-absorbing material is dopamine-modified magnetic wave-absorbing particles.
2. The wave absorbing carbon fiber prepreg of claim 1The material is characterized in that the magnetic wave-absorbing particles are Fe3O4Particles, Ni particles, Co particles and CoFe2O4The particle size of the magnetic wave-absorbing particles is preferably 10-100 nm, and the particle size of the dopamine modified magnetic wave-absorbing particles is preferably 15-105 nm.
3. The wave-absorbing carbon fiber prepreg according to claim 1, wherein the resin matrix in the wave-absorbing carbon fiber prepreg is 20-55% by weight, preferably 30-55% by weight, and preferably the wave-absorbing material in the resin matrix is 3-5% by weight.
4. The wave-absorbing carbon fiber prepreg according to claim 1, wherein the resin matrix is one or more of an epoxy resin matrix, a bismaleimide resin matrix and a cyanate ester resin matrix, and preferably the epoxy resin matrix is one or two of a Kunshan Yubo YPH-160 type hot-melt epoxy resin matrix and a Huibei new material R2300 type hot-melt epoxy resin matrix.
5. The wave-absorbing carbon fiber prepreg according to claim 1, wherein the area density of the carbon fibers is 150-250 g/m2Preferably, the surface density of the wave-absorbing carbon fiber prepreg is 280-360 g/m2。
6. A preparation method of the wave-absorbing carbon fiber prepreg according to any one of claims 1 to 5, wherein the preparation method comprises the following steps:
step S1, dispersing wave-absorbing materials in a molten resin matrix to form a mixture, wherein the wave-absorbing materials are dopamine-modified magnetic wave-absorbing particles;
and step S2, coating carbon fibers on the mixture to obtain the wave-absorbing carbon fiber prepreg.
7. The method for preparing a composite material according to claim 6, wherein the step S1 includes:
heating the resin matrix to form a molten resin matrix;
and stirring and mixing the wave-absorbing material and the molten resin matrix at the rotating speed of 40-100 rpm for 60-90 min to obtain the mixture.
8. The preparation method according to claim 6, further comprising a preparation process of the wave-absorbing material, wherein the preparation process of the wave-absorbing material comprises the following steps:
mixing the magnetic wave-absorbing particles with dopamine/Tris-HCl buffer solution at room temperature to form mixed solution;
carrying out ultrasonic treatment on the mixed solution for 30-60 min, and stirring for 24-36 h to obtain a modified system;
washing and drying the modified system to obtain the wave-absorbing material,
wherein the power of the ultrasonic is 150-250W, the stirring speed is 600-1200 rpm, and the drying temperature is 80-100 ℃.
9. The wave-absorbing carbon fiber reinforced plastic is prepared by curing the wave-absorbing carbon fiber prepreg according to any one of claims 1 to 5.
10. The wave-absorbing carbon fiber reinforced plastic according to claim 9, wherein the wave-absorbing carbon fiber reinforced plastic comprises one or more layers of the wave-absorbing carbon fiber prepreg which is stacked and cured by hot pressing.
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