CN113604133A - Light carbon-based electromagnetic shielding coating and preparation method thereof - Google Patents
Light carbon-based electromagnetic shielding coating and preparation method thereof Download PDFInfo
- Publication number
- CN113604133A CN113604133A CN202111007821.4A CN202111007821A CN113604133A CN 113604133 A CN113604133 A CN 113604133A CN 202111007821 A CN202111007821 A CN 202111007821A CN 113604133 A CN113604133 A CN 113604133A
- Authority
- CN
- China
- Prior art keywords
- electromagnetic shielding
- carbon
- coating
- graphene
- dimensional graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 122
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 87
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 87
- 239000000945 filler Substances 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000017 hydrogel Substances 0.000 claims description 24
- 230000004913 activation Effects 0.000 claims description 20
- 239000002518 antifoaming agent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 13
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 206010070834 Sensitisation Diseases 0.000 claims description 11
- 230000008313 sensitization Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 10
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 9
- 229930003268 Vitamin C Natural products 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 235000019154 vitamin C Nutrition 0.000 claims description 9
- 239000011718 vitamin C Substances 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 239000004964 aerogel Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 235000019800 disodium phosphate Nutrition 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 241000080590 Niso Species 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- -1 carbon nano tube alkene Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a light carbon-based electromagnetic shielding coating and a preparation method thereof, wherein the light carbon-based electromagnetic shielding coating comprises the following components in percentage by weight: electromagnetic shielding filler: 10% -25%, electromagnetic shielding filler dispersant: 2% -5%, polyurethane modified epoxy resin: 28% -40%, curing agent: 4% -8%, diluent: 25% -35%, auxiliary agent: 2% -5%; the electromagnetic shielding filler comprises one or two of three-dimensional graphene and nickel-plated carbon nanotubes. On the basis of the carbon-based electromagnetic shielding coating, the invention introduces metal Ni to construct Ni/C multi-element composite electromagnetic shielding filler, thereby achieving the purposes of keeping higher shielding efficiency of the metal electromagnetic shielding coating and reducing the density of the coating. In addition, the three-dimensional graphene is introduced into the Ni/C multi-element composite electromagnetic shielding filler, so that the surface density of the coating is further reduced, the uniform dispersion of the nickel-plated carbon nano tube in a resin system is promoted by virtue of the dispersion effect of the three-dimensional graphene, and the conductivity and the electromagnetic shielding performance of the coating are remarkably improved.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to an electromagnetic shielding coating, in particular to a light carbon-based electromagnetic shielding coating and a preparation method thereof.
Background
The rapid development of electronic information technology has led to a rapid increase in the number of various wireless communication devices and a significant increase in the frequency of use of electronic devices. They also generate a large amount of electromagnetic radiation while bringing convenience to the production and life of people. At present, electromagnetic radiation is listed as a fourth pollution source by the world health organization, and not only can irreversibly affect human health, but also can cause interference to normal operation of electronic equipment. The electromagnetic environment which is getting worse and worse is attracting wide attention of all countries, and the preparation of electromagnetic shielding materials with excellent performance is very important in both civil and military fields.
The electromagnetic interference means that electromagnetic signals emitted by the electronic and electrical equipment in operation disturb the normal operation of other surrounding electrical equipment and cause certain radiation damage to surrounding organisms. Electromagnetic shielding (EMI) refers to the situation where, in order to avoid electromagnetic interference and ensure good electromagnetic compatibility among electronic devices, certain conductive or magnetic materials are used to limit the electromagnetic wave energy in a specific space or control the electromagnetic radiation amount within a certain specified range, so as to ensure that electronic devices have a certain ability to resist external electromagnetic interference and do not radiate electromagnetic wave energy too much.
The traditional electromagnetic shielding material is mainly a metal sheet or a metal cover made of copper, iron and the like, and the metal material can concentrate magnetic flux on the surface of the material so as to prevent the transmission of electromagnetic waves. However, these materials have a large mass, are prone to corrosion, have a limited range of adjustment of shielding effectiveness, and their use temperature is often limited by the curie temperature, and cannot be used in high temperature environments. In addition, the shielding mechanism of the metal material is mainly reflection, and the electromagnetic wave pollution is not eliminated. Therefore, it is necessary to prepare a novel material with light weight, thin thickness, good environmental tolerance, excellent mechanical properties, and electromagnetic shielding properties and wave absorption properties.
At present, more and more researches are focused on the research of polymer-based electromagnetic shielding composite materials and electromagnetic shielding coatings. The polymer matrix material has little loss and reflection to electromagnetic wave, and the purpose of shielding electromagnetic wave is achieved by filling conductive filler in the polymer matrix material. The commonly used conductive fillers are of three types, one is a metal filler, a metal fiber or a metal nanoparticle; one is a conductive polymer; the other is a carbon-based filler. In contrast, carbon-based fillers are the most widely used, studied the most, and developed the fastest class of conductive fillers to date.
Common carbon shielding and wave absorbing fillers include carbon black, carbon fibers, carbon nanotubes, graphene, and the like. The graphene serving as a constituent unit of various carbon materials has the characteristics of small density, high electron mobility, good heat conduction and electric conductivity, excellent corrosion resistance and high temperature resistance, good mechanical properties and the like, and is widely researched and applied in various fields of wave absorption, electromagnetic shielding, heat conduction, electric conduction, energy storage and the like. However, after the graphene is filled in the resin to reach a certain concentration, van der waals force existing in the sheet layer enables the graphene to be easily agglomerated and stacked, so that the specific surface area of the graphene is greatly reduced, and the electromagnetic shielding performance of the coating is greatly influenced. Therefore, how to solve the agglomeration of graphene in the resin matrix becomes a great challenge for the development of the carbon-based electromagnetic shielding coating.
Disclosure of Invention
The invention provides a light carbon-based electromagnetic shielding coating and a preparation method thereof, which can solve the technical problems of large thickness, high density, poor temperature resistance and corrosion resistance, low shielding effectiveness and the like of the conventional electromagnetic shielding material.
The invention adopts the technical scheme that the light carbon-based electromagnetic shielding coating comprises the following components in percentage by weight: electromagnetic shielding filler: 10% -25%, electromagnetic shielding filler dispersant: 2% -5%, polyurethane modified epoxy resin: 28% -40%, curing agent: 4% -8%, diluent: 25% -35%, auxiliary agent: 2% -5%; the electromagnetic shielding filler comprises one or two of three-dimensional graphene and nickel-plated carbon nanotubes.
Further, the electromagnetic shielding filler dispersing agent is one or more of DS-172, AKN-2076, SY-2076 and AD 8301.
Further, the polyurethane modified epoxy resin comprises one or more of EPU-301, EPU-303 and EPU-133L.
Further, the curing agent comprises one or more of T-31, MH-112 and NX-2040.
Further, the thin material comprises one or more of butyl acetate, cyclohexanone, ethyl acetate and xylene.
Further, the auxiliary agent comprises a leveling agent and an antifoaming agent.
Further, the three-dimensional graphene is prepared by taking graphene as a raw material by a sol-gel method, and the preparation steps are as follows:
1) graphene pretreatment: in N2Carrying out heat treatment on the graphene at the temperature of more than 800 ℃ for 15-25 min under protection;
2) preparing three-dimensional graphene hydrogel: adding water into the pretreated graphene to prepare a solution, then adding vitamin C into the solution, continuously stirring the solution uniformly after dissolving, performing ultrasonic dispersion, and reacting the prepared solution in an oven at the temperature of 60-80 ℃ for 3-4 hours to obtain three-dimensional graphene hydrogel;
3) preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally putting the freeze-dried graphene aerogel into Ar at 1150-1250 DEG C2And carrying out heat treatment in the atmosphere for more than 2 hours to obtain the three-dimensional graphene.
Further, the nickel-plated carbon nanotube is obtained by plating metal nickel on the outer wall of the carbon nanotube by adopting a chemical plating process, and the preparation steps are as follows:
1) pretreating the carbon nano tube: in N2Placing the carbon nano tube above 800 ℃ for heat treatment for 15-25 min under protection;
2) surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into a mixed solution composed of stannous chloride and dilute hydrochloric acid, stirring for sensitization, filtering the carbon nano tube, washing with deionized water, and then putting the carbon nano tube into a mixed solution composed of palladium chloride and dilute hydrochloric acid, stirring for activation treatment;
3) nickel plating of the carbon nano tube: and (3) putting the sensitized and activated carbon nano tube into a nickel sulfate and sodium hydrogen phosphate solution at 70-90 ℃ for chemical nickel plating, continuously dropwise adding ammonia water to control the pH value of the solution to be 7.8 +/-0.2, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
The invention also relates to a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1, dissolving the polyurethane modified epoxy resin subjected to drying treatment by using a thinner, then adding the electromagnetic shielding filler, the electromagnetic shielding filler dispersing agent and the auxiliary agent while stirring, and dispersing uniformly to obtain an electromagnetic shielding filler dispersing solution; if the electromagnetic shielding fillers are multiple, respectively preparing electromagnetic shielding filler dispersion liquid;
s2, mixing the electromagnetic shielding filler dispersion liquid uniformly, adding a curing agent, and stirring uniformly to obtain the light carbon-based electromagnetic shielding coating.
Furthermore, when the raw materials in S1 are mixed to prepare the electromagnetic shielding filler dispersion liquid, the raw materials are dispersed for 15 to 20 minutes at the stirring speed of 500-600r/min, and the stirring time is 20 to 30 minutes after the curing agent is added in S2.
The invention has the following beneficial effects:
1. on the basis of the carbon-based electromagnetic shielding coating, the invention introduces metal Ni to construct Ni/C multi-element composite electromagnetic shielding filler, thereby achieving the purposes of keeping higher shielding efficiency of the metal electromagnetic shielding coating and reducing the density of the coating. In addition, the three-dimensional graphene is introduced into the Ni/C multi-element composite electromagnetic shielding filler, so that the surface density of the coating is further reduced, the uniform dispersion of the nickel-plated carbon nano tube in a resin system is promoted by virtue of the dispersion effect of the three-dimensional graphene, efficient electromagnetic transmission double network channels are formed in a resin matrix, and the conductivity and the electromagnetic shielding performance of the coating are remarkably improved.
2. When the three-dimensional graphene is prepared, the three-dimensional graphene is subjected to heat treatment, so that the content of organic groups on the surface of the graphene is reduced, the conductivity is improved, and the surface activation degree of the graphene is improved; then, the three-dimensional graphene is prepared by a sol-gel method, so that the technical problem that the two-dimensional graphene is seriously agglomerated due to van der Waals force is solved, and the electromagnetic shielding performance of the coating is improved.
3. The invention adopts the chemical plating process to successfully plate the metallic nickel on the outer wall of the carbon nano tube, so that the carbon nano tube has certain orientation in the dispersing and spraying processes, and the electrical property of the coating is improved.
4. The light carbon-based electromagnetic shielding coating prepared by the invention has the advantage of high shielding efficiency of a metal electromagnetic shielding coating, and has the characteristics of light weight and strong environment resistance of the carbon-based electromagnetic shielding coating. When the thickness of the coating is 0.05mm, the surface density is less than 50g/m2And the electromagnetic shielding effectiveness (8 GHz-12 GHz) exceeds 80dB, so that the requirements of commercial electromagnetic shielding materials are far met. The electromagnetic shielding coating is suitable for the civil field and the military field, can effectively improve the electromagnetic protection capability of weaponry, reduce the electromagnetic radiation of modern intelligent household appliances, and realize the wide application of the shielding coating in the aspects of military equipment, intelligent household appliances and the like.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1: a light carbon-based electromagnetic shielding coating comprises the following raw materials in percentage by weight:
electromagnetic shielding filler: 15% of electromagnetic shielding filler dispersing agent: 4%, polyurethane modified epoxy resin: 35% of curing agent: 6%, thinner 35%, and auxiliary agent: 5 percent.
Specifically, in the embodiment, the electromagnetic shielding filler is three-dimensional graphene and nickel-plated carbon nanotubes, wherein the three-dimensional graphene accounts for 10%, the nickel-plated carbon nanotubes accounts for 5%, the electromagnetic shielding filler dispersant is AD8301, the polyurethane modified epoxy resin is EPU-301, the curing agent is NX-2040 and MH-112, the NX-2040 accounts for 4%, the MH-112 accounts for 2%, the diluent is a mixed solvent of xylene, cyclohexanone and butyl acetate with a ratio of 3:3:1, the auxiliary agent includes two leveling agents and an antifoaming agent, the leveling agent is DN-2867, and the antifoaming agent is BYK-410.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1: graphene pretreatment: in N2And under protection, placing the graphene in a heating box at 800 ℃ for heat treatment for 20 minutes, reducing the content of organic groups on the surface of the graphene, improving the conductivity and improving the surface activation degree of the graphene.
S2, preparing the three-dimensional graphene hydrogel: adding water into the pretreated graphene to prepare a solution of 5g/L, adding vitamin C into the solution, continuously stirring the solution for 60 minutes after dissolving the vitamin C, and then ultrasonically dispersing the solution for 30 minutes at the temperature of 40 ℃. And (3) putting the dispersed solution into an oven at 70 ℃ for reaction for 3 hours to obtain the three-dimensional graphene hydrogel.
S3, preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water for 12 hours, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally putting the freeze-dried graphene aerogel into Ar at 1200 DEG C2And carrying out heat treatment for 2 hours in the atmosphere to obtain the three-dimensional graphene.
S4, preparing a three-dimensional graphene dispersion liquid: dissolving part of EPU-301 polyurethane modified epoxy resin subjected to drying treatment in xylene, cyclohexanone and butyl acetate according to the ratio of 3:3:1, adjusting a proper stirring speed, adding the prepared three-dimensional graphene, part of AD8301 type electromagnetic shielding filler dispersing agent, part of DN-2867 type flatting agent and BYK-410 type defoaming agent auxiliary agent while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the three-dimensional graphene dispersion liquid.
S5, pretreatment of the carbon nano tube: in N2Placing the carbon nano-tube under the protection of 800Heat treatment in a heating box at 20 ℃ for 20 minutes.
S6, surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into stannous chloride (SnCl)2·2H2O) and dilute hydrochloric acid (HCl) were slowly stirred for 15 minutes to sensitize. Filtering carbon nanotube, washing with deionized water, and adding palladium chloride (PdCl)2) The mixture solution was slowly stirred for 20 minutes with dilute hydrochloric acid to carry out the activation treatment.
S7, carbon nanotube nickel plating: putting the carbon nano tube after the sensitization and activation treatment into nickel sulfate (NiSO) at the temperature of 80 DEG C4·6H2O) and sodium hydrogen phosphate (NaH)2PO2·H2Chemical nickel plating is carried out in O) solution, and ammonia water (NH) is continuously dropped3·H2O) controlling the pH value of the solution to be 8.0, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
S8, preparing a nickel-plated carbon nanotube dispersion liquid: dissolving part of EPU-301 polyurethane modified epoxy resin subjected to drying treatment in xylene, cyclohexanone and butyl acetate according to the ratio of 3:3:1, adjusting a proper stirring speed, adding the prepared nickel-plated carbon nano tube, part of AD8301 type electromagnetic shielding filler dispersing agent, part of DN-2867 type flatting agent and BYK-410 type defoaming agent auxiliary agent while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the nickel-plated carbon nano tube alkene dispersion liquid.
S9, preparing electromagnetic shielding paint: and mixing and stirring the uniformly dispersed three-dimensional graphene dispersion liquid and the nickel-plated carbon nanotube dispersion liquid, adding NX-2040 type and MH-112 type curing agents in proportion, and finally stirring for 15 minutes to obtain the light carbon-based electromagnetic shielding coating prepared by the invention.
Embodiment 2 a light carbon-based electromagnetic shielding coating comprises the following raw materials by weight:
electromagnetic shielding filler: 20% of electromagnetic shielding filler dispersing agent: 3% of polyurethane modified epoxy resin: 34% of a curing agent: 6%, thinner 33%, auxiliary agent: 4 percent.
In the embodiment of the application, the electromagnetic shielding filler is three-dimensional graphene and nickel-plated carbon nanotubes, wherein the three-dimensional graphene accounts for 5%, the nickel-plated carbon nanotubes accounts for 15%, the electromagnetic shielding filler dispersing agent is SY-2076, the polyurethane modified epoxy resin accounts for EPU-301, the curing agent is NX-2040 and MH-112, the NX-2040 accounts for 4%, the MH-112 accounts for 2%, the thinner accounts for a mixed solvent of xylene, cyclohexanone and butyl acetate with a ratio of 4:1:1, the auxiliary agent comprises two types of a leveling agent and an antifoaming agent, the leveling agent is BYK-333, and the antifoaming agent is BYK-410.
Based on the same inventive concept, the embodiment also provides a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1: graphene pretreatment: in N2And under protection, placing the graphene in a 820 ℃ heating box for heat treatment for 15 minutes, reducing the content of organic groups on the surface of the graphene, improving the conductivity and improving the surface activation degree of the graphene.
S2, preparing the three-dimensional graphene hydrogel: preparing the pretreated graphene into a solution of 5g/L, adding vitamin C into the solution, continuously stirring for 50 minutes after dissolving, and then ultrasonically dispersing for 30 minutes at 35 ℃. And (3) putting the dispersed solution into an oven at 80 ℃ for reaction for 3.5 hours to obtain the three-dimensional graphene hydrogel.
S3, preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water for 12 hours, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally putting the freeze-dried graphene aerogel into Ar at 1150 DEG C2And carrying out heat treatment for 2.5 hours in the atmosphere to obtain the three-dimensional graphene.
S4, preparing a three-dimensional graphene dispersion liquid: dissolving a part of dried EPU-301 type polyurethane modified epoxy resin into a thin material composed of dimethylbenzene, cyclohexanone and butyl acetate according to a ratio of 4:1:1, adjusting a proper stirring speed, adding the prepared three-dimensional graphene, a part of SY-2076 type electromagnetic shielding filler dispersing agent, a part of BYK-333 type flatting agent, a BYK-410 type defoaming agent and other auxiliary agents while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the three-dimensional graphene dispersion liquid.
S5 carbon nanotube pre-treatmentAnd (3) treatment: in N2The carbon nano tube is placed in a heating box at 800 ℃ for heat treatment for 20 minutes under protection.
S6, surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into stannous chloride (SnCl)2·2H2O) and dilute hydrochloric acid (HCl) for 20 minutes to sensitize. Filtering carbon nanotube, washing with deionized water, and adding palladium chloride (PdCl)2) The mixture was slowly stirred for 15 minutes with dilute hydrochloric acid to carry out the activation treatment.
S7, carbon nanotube nickel plating: putting the sensitized and activated carbon nano tube into nickel sulfate (NiSO) at 85 DEG C4·6H2O) and sodium hydrogen phosphate (NaH)2PO2·H2Chemical nickel plating is carried out in O) solution, and ammonia water (NH) is continuously dropped3·H2O) controlling the pH value of the solution to be 8.2, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
S8, preparing a nickel-plated carbon nanotube dispersion liquid: dissolving part of the dried EPU-301 polyurethane modified epoxy resin into a thin material composed of dimethylbenzene, cyclohexanone and butyl acetate according to the ratio of 4:1:1, adjusting a proper stirring speed, adding the prepared nickel-plated carbon nano tube, part of SY-2076 type electromagnetic shielding filler dispersing agent, part of BYK-333 type flatting agent, BYK-410 type defoaming agent and other auxiliary agents while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the nickel-plated carbon nano tube alkene dispersing solution.
S9, preparing electromagnetic shielding paint: and mixing and stirring the uniformly dispersed three-dimensional graphene dispersion liquid and the nickel-plated carbon nanotube dispersion liquid, adding NX-2040 type and MH-112 type curing agents in proportion, and finally stirring for 15 minutes to obtain the light carbon-based electromagnetic shielding coating prepared by the invention.
Embodiment 3 a light carbon-based electromagnetic shielding coating comprises the following raw materials by weight:
electromagnetic shielding filler: 25% of electromagnetic shielding filler dispersing agent: 4%, polyurethane modified epoxy resin: 28% of curing agent: 4%, thinner 35%, and auxiliary agent: 4 percent.
In the embodiment of the application, the electromagnetic shielding filler is three-dimensional graphene and nickel-plated carbon nanotubes, wherein the three-dimensional graphene accounts for 10%, the nickel-plated carbon nanotubes accounts for 15%, the electromagnetic shielding filler dispersing agent is SY-2076, the polyurethane modified epoxy resin is EPU-133L, the curing agent is NX-2040 and MH-112, the NX-2040 accounts for 2%, the MH-112 accounts for 2%, the thinner is a mixed solvent of xylene, cyclohexanone and butyl acetate with the proportion of 3:3:1, the auxiliary agent comprises two of a leveling agent and an antifoaming agent, the leveling agent is BYK-333, and the antifoaming agent is BYK-410.
The embodiment of the application also provides a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1: graphene pretreatment: in N2And under protection, placing the graphene in a heating box at 800 ℃ for heat treatment for 20 minutes, reducing the content of organic groups on the surface of the graphene, improving the conductivity and improving the surface activation degree of the graphene.
S2, preparing the three-dimensional graphene hydrogel: preparing the pretreated graphene into a solution of 5g/L, adding vitamin C into the solution, continuously stirring the solution for 60 minutes after dissolving the vitamin C, and then ultrasonically dispersing the solution for 30 minutes at the temperature of 40 ℃. And (3) putting the dispersed solution into an oven at 70 ℃ for reaction for 3.5 hours to obtain the three-dimensional graphene hydrogel.
S3, preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water for 12 hours, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally putting the freeze-dried graphene aerogel into Ar at 1200 DEG C2And carrying out heat treatment for 2 hours in the atmosphere to obtain the three-dimensional graphene.
S4, preparing a three-dimensional graphene dispersion liquid: dissolving part of EPU-133L type polyurethane modified epoxy resin subjected to drying treatment in xylene, cyclohexanone and butyl acetate according to the proportion of 3:3:1, adjusting a proper stirring speed, adding the prepared three-dimensional graphene, part of SY-2076 type electromagnetic shielding filler dispersing agent, part of BYK-333 type flatting agent, BYK-410 type defoaming agent and other auxiliaries while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the three-dimensional graphene dispersion liquid.
S5, pretreatment of the carbon nano tube: in N2The carbon nano tube is placed in a heating box at 800 ℃ for heat treatment for 20 minutes under protection.
S6, surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into stannous chloride (SnCl)2·2H2O) and dilute hydrochloric acid (HCl) were slowly stirred for 15 minutes to sensitize. Filtering carbon nanotube, washing with deionized water, and adding palladium chloride (PdCl)2) The mixture solution was slowly stirred for 20 minutes with dilute hydrochloric acid to carry out the activation treatment.
S7, carbon nanotube nickel plating: putting the carbon nano tube after the sensitization and activation treatment into nickel sulfate (NiSO) at the temperature of 80 DEG C4·6H2O) and sodium hydrogen phosphate (NaH)2PO2·H2Chemical nickel plating is carried out in O) solution, and ammonia water (NH) is continuously dropped3·H2O) controlling the pH value of the solution to be 8.0, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
S8, preparing a nickel-plated carbon nanotube dispersion liquid: dissolving part of EPU-133L type polyurethane modified epoxy resin subjected to drying treatment in xylene, cyclohexanone and butyl acetate according to the proportion of 3:3:1, adjusting a proper stirring speed, adding the prepared nickel-plated carbon nano tube, part of SY-2076 type electromagnetic shielding filler dispersing agent, part of BYK-333 type flatting agent, BYK-410 type defoaming agent and other auxiliary agents while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the nickel-plated carbon nano tube alkene dispersion liquid.
S9, preparing electromagnetic shielding paint: and mixing and stirring the uniformly dispersed three-dimensional graphene dispersion liquid and the nickel-plated carbon nanotube dispersion liquid, adding NX-2040 type and MH-112 type curing agents in proportion, and finally stirring for 15 minutes to obtain the light carbon-based electromagnetic shielding coating prepared by the invention.
Comparative example 1
A light carbon-based electromagnetic shielding coating comprises the following raw materials in percentage by weight:
electromagnetic shielding filler: 10% of electromagnetic shielding filler dispersing agent: 4%, polyurethane modified epoxy resin: 40% and a curing agent: 8% of diluent: 33% and auxiliary agent: 5 percent.
In the embodiment, the electromagnetic shielding filler is three-dimensional graphene, the dispersing agent of the electromagnetic shielding filler is DS-172, the polyurethane modified epoxy resin is EPU-301, the curing agent is NX-2040, the thinner is a mixed solvent of xylene and cyclohexanone in a ratio of 4:3, the auxiliary agent comprises a leveling agent and an antifoaming agent, wherein the leveling agent is DN-2867, and the antifoaming agent is BYK-410.
The embodiment of the application also provides a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1: graphene pretreatment: in N2And under protection, placing the graphene in a heating box at 800 ℃ for heat treatment for 20 minutes, reducing the content of organic groups on the surface of the graphene, improving the conductivity and improving the surface activation degree of the graphene.
S2, preparing the three-dimensional graphene hydrogel: preparing the pretreated graphene into a solution of 5g/L, adding vitamin C into the solution, continuously stirring the solution for 60 minutes after dissolving the vitamin C, and then ultrasonically dispersing the solution for 30 minutes at the temperature of 40 ℃. And (3) putting the dispersed solution into an oven at 70 ℃ for reaction for 3 hours to obtain the three-dimensional graphene hydrogel.
S3, preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water for 12 hours, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally putting the freeze-dried graphene aerogel into Ar at 1200 DEG C2And carrying out heat treatment for 2 hours in the atmosphere to obtain the three-dimensional graphene.
S4, preparing a three-dimensional graphene dispersion liquid: dissolving the dried EPU-301 type polyurethane modified epoxy resin into a thin material composed of dimethylbenzene and cyclohexanone according to a ratio of 4:3, adjusting a proper stirring speed, adding the prepared three-dimensional graphene, the DS-172 type electromagnetic shielding filler dispersing agent, the DN-2867 type flatting agent, the BYK-410 type defoaming agent and other auxiliaries while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the three-dimensional graphene dispersion liquid.
S5, preparing electromagnetic shielding paint: adding an NX-2040 type curing agent into the uniformly dispersed three-dimensional graphene dispersion liquid, and stirring for 15 minutes to obtain the light carbon-based electromagnetic shielding coating prepared by the invention.
Comparative example 2
A light carbon-based electromagnetic shielding coating comprises the following raw materials in percentage by weight:
electromagnetic shielding filler: 15% of electromagnetic shielding filler dispersing agent: 3% of polyurethane modified epoxy resin: 40% and a curing agent: 8% of diluent: 30% and auxiliary agent: 4 percent.
In the embodiment, the electromagnetic shielding filler is a nickel-plated carbon nanotube, the dispersing agent of the electromagnetic shielding filler is DS-172, the polyurethane modified epoxy resin is EPU-303, the curing agent is NX-2040, the thinner is a mixed solvent of xylene, cyclohexanone and butyl acetate with the proportion of 3:3:1, the auxiliary agent comprises a leveling agent and an antifoaming agent, wherein the leveling agent is BYK-333, and the antifoaming agent is BYK-410.
The embodiment also provides a preparation method of the light carbon-based electromagnetic shielding coating, which comprises the following steps:
s1, pretreatment of the carbon nano tube: in N2The carbon nano tube is placed in a heating box at 800 ℃ for heat treatment for 20 minutes under protection.
S2, surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into stannous chloride (SnCl)2·2H2O) and dilute hydrochloric acid (HCl) were slowly stirred for 15 minutes to sensitize. Filtering carbon nanotube, washing with deionized water, and adding palladium chloride (PdCl)2) The mixture solution was slowly stirred for 20 minutes with dilute hydrochloric acid to carry out the activation treatment.
S3, carbon nanotube nickel plating: putting the carbon nano tube after the sensitization and activation treatment into nickel sulfate (NiSO) at the temperature of 80 DEG C4·6H2O) and sodium hydrogen phosphate (NaH)2PO2·H2Chemical nickel plating is carried out in O) solution, and ammonia water (NH) is continuously dropped3·H2O) controlling the pH value of the solution to be 7.8, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
S4, preparing a nickel-plated carbon nanotube dispersion liquid: dissolving the dried EPU-303 type polyurethane modified epoxy resin in xylene, cyclohexanone and butyl acetate according to the proportion of 3:3:1, adjusting a proper stirring speed, adding the prepared nickel-plated carbon nano tube, the DS-172 type electromagnetic shielding filler dispersing agent, the BYK-333 type leveling agent, the BYK-410 type defoaming agent and other auxiliary agents while stirring, and continuously dispersing for 20 minutes at a fixed stirring speed after the addition is finished to obtain the nickel-plated carbon nano tube alkene dispersion liquid.
S5, preparing electromagnetic shielding paint: adding NX-2040 type curing agent into the uniformly dispersed nickel-plated carbon nanotube dispersion liquid, and stirring for 15 minutes to obtain the light carbon-based electromagnetic shielding coating prepared by the invention.
The light multi-element electromagnetic shielding coatings prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for thickness, areal density, shielding effectiveness, conductivity, and other properties, and the results are shown in table 1 below. The test methods used in examples 1-3 and comparative examples 1-2 were as follows:
(1) coating surface density test mode:
weighing the substrate plate mass, denoted M1And the area is marked as S, after the wave-absorbing coating is sprayed and cured on the substrate board, the weighing mass is marked as M2The surface density of the wave-absorbing coating is calculated according to the following formula.
(2) Coating shielding effectiveness test mode:
and testing the shielding effectiveness of the coating by adopting a NA7500 type vector network analyzer according to the test standard of ASTM D4935-10.
(3) Coating conductivity test mode:
after the sample is placed at room temperature for a period of time, the conductivity of the coating is tested by a four-probe method, the distance between four probes is 1mm, the test is carried out for 6 times in parallel, and the average value is taken.
TABLE 1 results of performance tests of barrier coatings prepared in different examples and comparative examples
As can be seen from table 1 above, the lightweight carbon-based electromagnetic shielding coating prepared by the present invention has very low areal density, and at the same time, has excellent shielding effectiveness and conductivity. When the thickness of the coating is 0.05mm, the surface density of the coating is less than 50 g.m-2The electromagnetic shielding effectiveness of 8 GHz-12 GHz can reach more than 80dB, and the electric conductivity is close to 20S/cm. In contrast, the introduction of the metal layer greatly improves the conductivity of the carbon-based material, and as can be seen from comparative example 1 and comparative example 2, the conductivity of the nickel-plated carbon nanotube is significantly better than that of the three-dimensional graphene. The three-dimensional graphene is introduced into the nickel-plated carbon nanotube dispersion liquid, so that on one hand, the uniform dispersion of the nickel-plated carbon nanotube in a resin system is promoted by virtue of the dispersion effect of the three-dimensional graphene, and the three-dimensional graphene and the resin matrix form an efficient electromagnetic transmission dual network channel, so that the conductivity of the nickel-plated carbon nanotube and the electromagnetic shielding performance of a coating are remarkably improved. In addition, the specific surface area of the material is effectively increased by the porous structure of the three-dimensional graphene, and the transmission distance of electromagnetic waves is increased when the electromagnetic waves are continuously reflected on the hole wall when being transmitted in the three-dimensional directional holes, so that the electromagnetic wave energy is subjected to multiple reflections in an electromagnetic field and is finally lost in the form of heat energy. It can be seen from comparison of example 3, comparative example 1 and comparative example 2 that the addition of three-dimensional graphene to the nickel-plated carbon nanotubes significantly improves the conductivity and shielding effectiveness of the coating. On the other hand, the density of the three-dimensional graphene is extremely low, and the addition of the three-dimensional graphene can greatly reduce the surface density of the coating, so that the development requirement of light weight of the electromagnetic shielding material is met.
Claims (10)
1. The light carbon-based electromagnetic shielding coating is characterized by comprising the following components in percentage by weight: electromagnetic shielding filler: 10% -25%, electromagnetic shielding filler dispersant: 2% -5%, polyurethane modified epoxy resin: 28% -40%, curing agent: 4% -8%, diluent: 25% -35%, auxiliary agent: 2% -5%; the electromagnetic shielding filler comprises one or two of three-dimensional graphene and nickel-plated carbon nanotubes.
2. The lightweight carbon-based electromagnetic shielding paint according to claim 1, wherein: the electromagnetic shielding filler dispersing agent is one or more of DS-172, AKN-2076, SY-2076 and AD 8301.
3. The lightweight carbon-based electromagnetic shielding paint according to claim 1, wherein: the polyurethane modified epoxy resin comprises one or more of EPU-301, EPU-303 and EPU-133L.
4. The lightweight carbon-based electromagnetic shielding paint according to claim 1, wherein: the curing agent comprises one or more of T-31, MH-112 and NX-2040.
5. The lightweight carbon-based electromagnetic shielding paint according to claim 1, wherein: the thin material comprises one or more of butyl acetate, cyclohexanone, ethyl acetate and xylene.
6. The lightweight carbon-based electromagnetic shielding paint according to claim 1, wherein: the auxiliary agent comprises a leveling agent and an antifoaming agent.
7. The light carbon-based electromagnetic shielding coating as claimed in any one of claims 1 to 6, wherein the three-dimensional graphene is prepared from graphene by a sol-gel method, and the preparation steps are as follows:
1) graphene pretreatment: in N2Carrying out heat treatment on the graphene at the temperature of more than 800 ℃ for 15-25 min under protection;
2) preparing three-dimensional graphene hydrogel: adding water into the pretreated graphene to prepare a solution, then adding vitamin C into the solution, continuously stirring the solution uniformly after dissolving, performing ultrasonic dispersion, and reacting the prepared solution in an oven at the temperature of 60-80 ℃ for 3-4 hours to obtain three-dimensional graphene hydrogel;
3) preparing three-dimensional graphene: freezing the three-dimensional graphene hydrogel washed by distilled water, then putting the three-dimensional graphene hydrogel into a freeze dryer for freeze drying, and finally freeze dryingSubjecting the graphene aerogel to Ar at 1150-1250 DEG C2And carrying out heat treatment in the atmosphere for more than 2 hours to obtain the three-dimensional graphene.
8. The light-weight carbon-based electromagnetic shielding coating as claimed in any one of claims 1 to 6, wherein the nickel-plated carbon nanotube is obtained by plating metal nickel on the outer wall of the carbon nanotube by a chemical plating process, and the preparation steps are as follows:
1) pretreating the carbon nano tube: in N2Placing the carbon nano tube above 800 ℃ for heat treatment for 15-25 min under protection;
2) surface sensitization and activation of the carbon nano tube: putting the pretreated carbon nano tube into a mixed solution composed of stannous chloride and dilute hydrochloric acid, stirring for sensitization, filtering the carbon nano tube, washing with deionized water, and then putting the carbon nano tube into a mixed solution composed of palladium chloride and dilute hydrochloric acid, stirring for activation treatment;
3) nickel plating of the carbon nano tube: and (3) putting the sensitized and activated carbon nano tube into a nickel sulfate and sodium hydrogen phosphate solution at 70-90 ℃ for chemical nickel plating, continuously dropwise adding ammonia water to control the pH value of the solution to be 7.8 +/-0.2, filtering, washing and drying to obtain the nickel-plated carbon nano tube.
9. The preparation method of the lightweight carbon-based electromagnetic shielding coating of any one of claims 1 to 8, characterized by comprising the following steps:
s1, dissolving the polyurethane modified epoxy resin subjected to drying treatment by using a thinner, then adding the electromagnetic shielding filler, the electromagnetic shielding filler dispersing agent and the auxiliary agent while stirring, and dispersing uniformly to obtain an electromagnetic shielding filler dispersing solution; if the electromagnetic shielding fillers are multiple, respectively preparing electromagnetic shielding filler dispersion liquid;
s2, mixing the electromagnetic shielding filler dispersion liquid uniformly, adding a curing agent, and stirring uniformly to obtain the light carbon-based electromagnetic shielding coating.
10. The preparation method of the lightweight carbon-based electromagnetic shielding coating according to claim 9, wherein: when the raw materials in the S1 are mixed to prepare the electromagnetic shielding filler dispersion liquid, the dispersion liquid is dispersed for 15 to 20 minutes at the stirring speed of 500-600r/min, and in the S2, the stirring time is 20 to 30 minutes after the curing agent is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111007821.4A CN113604133A (en) | 2021-08-30 | 2021-08-30 | Light carbon-based electromagnetic shielding coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111007821.4A CN113604133A (en) | 2021-08-30 | 2021-08-30 | Light carbon-based electromagnetic shielding coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113604133A true CN113604133A (en) | 2021-11-05 |
Family
ID=78342305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111007821.4A Pending CN113604133A (en) | 2021-08-30 | 2021-08-30 | Light carbon-based electromagnetic shielding coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113604133A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621299A (en) * | 2021-09-08 | 2021-11-09 | 青岛九维华盾科技研究院有限公司 | Light broadband electromagnetic shielding coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045533A (en) * | 2007-03-12 | 2007-10-03 | 清华大学 | Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof |
| CN101275052A (en) * | 2008-05-14 | 2008-10-01 | 海洋化工研究院 | Corrosion-resistant electromagnetic screen coating and preparation thereof |
| CN102766304A (en) * | 2012-07-31 | 2012-11-07 | 上海交通大学 | Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof |
| CN103317734A (en) * | 2012-03-20 | 2013-09-25 | 沈阳航空航天大学 | Method for preparing radar wave-absorbing composite material based on carbon nanometer film |
| CN108439371A (en) * | 2016-12-13 | 2018-08-24 | 无锡格致新材料研发科技有限公司 | A kind of preparation method of three-dimensional (3D) graphene |
| CN110484097A (en) * | 2019-09-23 | 2019-11-22 | 西南交通大学 | A kind of composite electromagnetic screen conductive coating and preparation method thereof and application method |
| CN110951369A (en) * | 2019-12-12 | 2020-04-03 | 深圳市利红金科技有限公司 | Coating for electromagnetic shielding, preparation method and use method |
-
2021
- 2021-08-30 CN CN202111007821.4A patent/CN113604133A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045533A (en) * | 2007-03-12 | 2007-10-03 | 清华大学 | Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof |
| CN101275052A (en) * | 2008-05-14 | 2008-10-01 | 海洋化工研究院 | Corrosion-resistant electromagnetic screen coating and preparation thereof |
| CN103317734A (en) * | 2012-03-20 | 2013-09-25 | 沈阳航空航天大学 | Method for preparing radar wave-absorbing composite material based on carbon nanometer film |
| CN102766304A (en) * | 2012-07-31 | 2012-11-07 | 上海交通大学 | Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof |
| CN108439371A (en) * | 2016-12-13 | 2018-08-24 | 无锡格致新材料研发科技有限公司 | A kind of preparation method of three-dimensional (3D) graphene |
| CN110484097A (en) * | 2019-09-23 | 2019-11-22 | 西南交通大学 | A kind of composite electromagnetic screen conductive coating and preparation method thereof and application method |
| CN110951369A (en) * | 2019-12-12 | 2020-04-03 | 深圳市利红金科技有限公司 | Coating for electromagnetic shielding, preparation method and use method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621299A (en) * | 2021-09-08 | 2021-11-09 | 青岛九维华盾科技研究院有限公司 | Light broadband electromagnetic shielding coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Multilayer-structured Ni-Co-Fe-P/polyaniline/polyimide composite fabric for robust electromagnetic shielding with low reflection characteristic | |
| Liu et al. | Preparation and properties of cobalt oxides coated carbon fibers as microwave-absorbing materials | |
| CN107949266B (en) | A kind of three-dimensional porous flower-like structure cobalt/carbon nano composite electromagnetic wave absorption material and preparation method thereof | |
| Wang et al. | Layer-by-layer assembly of PDMS-coated nickel ferrite/multiwalled carbon nanotubes/cotton fabrics for robust and durable electromagnetic interference shielding | |
| Li et al. | Ti3C2Tx/PANI/liquid metal composite microspheres with 3D nanoflower structure: preparation, characterization, and applications in EMI shielding | |
| Chen et al. | Preparation and microwave absorbing properties of nickel-coated carbon fiber with polyaniline via in situ polymerization | |
| CN105950112B (en) | A kind of nano combined absorbing material and preparation method thereof | |
| CN207885101U (en) | A kind of electromagnetic shielding film | |
| Feng et al. | Enhanced electromagnetic microwave absorption of Fe/C/SiCN composite ceramics targeting in integrated structure and function | |
| CN110846881A (en) | Co3O4Preparation method of/PANI/MXene/PI electromagnetic shielding fabric | |
| Cheng et al. | Preparation of silver/carbon fiber/polyaniline microwave absorption composite and its application in epoxy resin | |
| CN111410194B (en) | Composite electromagnetic wave-absorbing foam prepared from ZIF-67/melamine and preparation method thereof | |
| CN112777582B (en) | Preparation method of nitrogen-doped ordered mesoporous carbon/cobalt metal composite material | |
| Zhai et al. | Facile synthesis of nickel/reduced graphene oxide-coated glass fabric for highly efficient electromagnetic interference shielding | |
| CN109896520A (en) | A kind of magnetizing reduction stannic oxide/graphene nano composite material and preparation method and application | |
| CN109181637A (en) | A kind of lamination shape Mo2CTx/ nitrogen-doped carbon micro-nano hybridization compounding absorbing material and preparation method thereof | |
| CN113604133A (en) | Light carbon-based electromagnetic shielding coating and preparation method thereof | |
| Li et al. | Electrostatic self-assembly sandwich-like 2D/2D NiFe-LDH/MXene heterostructure for strong microwave absorption | |
| CN107434857B (en) | Graphene-loaded cerium oxide and rubber composite material and preparation method thereof | |
| CN110498990B (en) | Preparation method of C @ Ni composite material and electromagnetic shielding film | |
| CN107903435A (en) | A kind of anti-electromagnetic radiation waterproof breathable membrane material and preparation method and application | |
| Chen et al. | Preparation and characterization of CIP@ Fe3O4@ PANI composites | |
| Liu et al. | Multifunctional Nd2O3/CNFs composite for microwave absorption and anti-corrosion applications | |
| Dai et al. | Facile synthesis of polypyrrole nanoparticles with tunable conductivity for efficient electromagnetic wave absorption and shielding performance | |
| CN106854453A (en) | A kind of preparation method of lamellar composite absorbing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211105 |