CN114685936A - Graphene-based wave-absorbing honeycomb and preparation method thereof - Google Patents
Graphene-based wave-absorbing honeycomb and preparation method thereof Download PDFInfo
- Publication number
- CN114685936A CN114685936A CN202011565263.9A CN202011565263A CN114685936A CN 114685936 A CN114685936 A CN 114685936A CN 202011565263 A CN202011565263 A CN 202011565263A CN 114685936 A CN114685936 A CN 114685936A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- absorbing
- based wave
- wave
- 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 146
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 47
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 47
- 239000011162 core material Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 230000007306 turnover Effects 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007766 curtain coating Methods 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- QCGKUFZYSPBMAY-UHFFFAOYSA-N methyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C(C(=O)OC)CCC2OC21 QCGKUFZYSPBMAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000011358 absorbing material Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 6
- 239000004760 aramid Substances 0.000 description 5
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alicyclic olefin Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002592 echocardiography Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CKZMMOFDBUAGTN-UHFFFAOYSA-N n,n-dimethylformamide;n-methylformamide Chemical compound CNC=O.CN(C)C=O CKZMMOFDBUAGTN-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The embodiment of the invention provides a graphene-based wave-absorbing honeycomb and a preparation method thereof; the preparation method comprises the following steps: a) mixing tubular graphene, alicyclic epoxy resin and an organic solvent, and then grinding to obtain tubular graphene/alicyclic epoxy resin; b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb. Compared with the prior art, the preparation method provided by the invention has the advantages that the tubular graphene/alicyclic epoxy resin with specific components is coated on the hole wall of the honeycomb core material and then dried to obtain the graphene-based wave-absorbing honeycomb, so that the process is simple, the energy consumption is low, and the production and manufacturing period is short; the prepared graphene-based wave-absorbing honeycomb is stable in structure, good in electric conduction and heat conduction performance, light in weight, high in strength and good in wave-absorbing performance, and is suitable for being applied to radar stealth materials.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a graphene-based wave-absorbing honeycomb and a preparation method thereof.
Background
With the rapid development of information technology, various stealth technologies have been widely applied to various stealth weapons such as stealth airplanes, stealth missiles, and stealth armored vehicles. At present, the radar stealth technology is still an important stealth technology of weaponry, the shape design of the weaponry and other stealth technologies are high in cost and complex in technology, and therefore stealth materials are widely regarded as the main technology of radar stealth. The radar stealth material is a material capable of absorbing radar waves and obviously attenuating the strength of target echoes, and the main purpose of the radar stealth material is to reduce the scattering cross section of radar. The radar structure wave-absorbing material has double functions of bearing and stealth, becomes an important research field of radar wave stealth materials, and as an important component of the radar stealth materials, various absorbents also become the key points of research of people.
The wave-absorbing honeycomb is a middle core material of a radar stealth material or a composite wave-absorbing material, the functionality of the wave-absorbing honeycomb has decisive influence on the wave transmission and wave-absorbing performance of the composite material, and the key point for realizing the functionality of the wave-absorbing honeycomb lies in the development of a functional resin system and a wave-absorbing agent and the development of the process of the functional resin system and the wave-absorbing agent. The wave-absorbing honeycomb sandwich structure is more and more favored by research personnel of wave-absorbing materials due to excellent performance and strong designability, so that domestic and foreign scholars and research personnel increasingly pay attention to the wave-absorbing honeycomb functional research and become the research focus and development direction of the wave-absorbing materials.
For example, the chinese patent with publication number CN110054182A discloses a magnetic graphene-based wave-absorbing honeycomb material and a preparation method thereof, the magnetic graphene-based wave-absorbing honeycomb material provided by the invention is a structural wave-absorbing material formed by uniformly dispersing magnetic graphene oxide in a honeycomb core material; the preparation method comprises the following steps: s1, preparing a magnetic graphene oxide radar wave absorbent; s2, stably dispersing the magnetic graphene oxide radar wave absorbent in an organic solvent to form absorbent dispersion liquid; s3, putting the honeycomb core material into the absorbent dispersion liquid for dipping; s4, drying and curing the impregnated honeycomb core material to obtain the honeycomb core materialTo the magnetic graphene-based wave-absorbing honeycomb material. However, in the invention, magnetic graphene oxide needs to be prepared firstly, the preparation of the magnetic graphene oxide is to oxidize natural graphite flakes serving as raw materials by a Hummers method to obtain graphene oxide, and the obtained graphene oxide is then mixed with ethylene glycol and FeCl3Mixing sodium acetate and ethylenediamine, carrying out hydrothermal reaction, and then carrying out vacuum drying to obtain a magnetic graphene oxide absorbent; and then the magnetic graphene-based wave-absorbing honeycomb material is prepared, so that the overall process is complex, the energy consumption is high, the production and manufacturing period is long, and the product performance is poor.
Disclosure of Invention
In view of the above, the invention aims to provide a graphene-based wave-absorbing honeycomb and a preparation method and application thereof, the preparation method provided by the invention has the advantages of simple process, low energy consumption and short production and manufacturing period, and the prepared graphene-based wave-absorbing honeycomb has the advantages of stable structure, good electric conductivity and heat conductivity, light weight, high strength and good wave-absorbing performance.
The invention provides a preparation method of a graphene-based wave-absorbing honeycomb, which comprises the following steps:
a) mixing tubular graphene, alicyclic epoxy resin and an organic solvent, and then grinding to obtain tubular graphene/alicyclic epoxy resin;
b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb.
Preferably, the organic solvent is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC).
Preferably, the tubular graphene is single-walled tubular graphene (SWNT) or multi-walled tubular graphene (MWNT).
Preferably, the cycloaliphatic epoxy resin is selected from one or more of methyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate.
Preferably, the organic solvent is N, N-dimethylformamide, and the mass ratio of the tubular graphene, the alicyclic epoxy resin and the N, N-dimethylformamide in the step a) is (1-3): 40: (57-59).
Preferably, the rotation speed of the grinding treatment in the step a) is 500 rpm-1500 rpm, and the time is 0.5 h-1 h.
Preferably, the fineness of the tubular graphene/alicyclic epoxy resin in step a) is less than or equal to 20 μm.
Preferably, the coating in step b) is by curtain coating, dip coating or spray coating.
Preferably, the drying process in step b) specifically comprises:
and (3) placing the coated honeycomb core material in a vacuum oven, and performing turnover deposition by taking the T direction as a central axis, wherein the rotating speed is 20-40 rpm, the temperature is 100-200 ℃, and the heat preservation time is 1-3 h.
The invention also provides a graphene-based wave-absorbing honeycomb which is prepared by the preparation method of the technical scheme.
The invention also provides application of the wave-absorbing honeycomb in radar stealth materials, wherein the wave-absorbing honeycomb is the graphene-based wave-absorbing honeycomb in the technical scheme.
The invention provides a graphene-based wave-absorbing honeycomb and a preparation method thereof; the preparation method comprises the following steps: a) mixing tubular graphene, alicyclic epoxy resin and an organic solvent, and then grinding to obtain tubular graphene/alicyclic epoxy resin; b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb. Compared with the prior art, the preparation method provided by the invention has the advantages that the tubular graphene/alicyclic epoxy resin with specific components is coated on the hole wall of the honeycomb core material and then dried to obtain the graphene-based wave-absorbing honeycomb, the process is simple, the energy consumption is low, and the production and manufacturing period is short; the prepared graphene-based wave-absorbing honeycomb is stable in structure, good in electric conduction and heat conduction performance, light in weight, high in strength and good in wave-absorbing performance, and is suitable for being applied to radar stealth materials.
Drawings
Fig. 1 is a schematic structural diagram of a graphene-based wave-absorbing honeycomb core material obtained by a preparation method provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a graphene-based wave-absorbing honeycomb, which comprises the following steps:
a) mixing tubular graphene, alicyclic epoxy resin and N, N-dimethylformamide, and then grinding to obtain tubular graphene/alicyclic epoxy resin;
b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb.
Tubular graphene, alicyclic epoxy resin and N-methyl formamide N, N-dimethyl formamide are mixed and then ground to obtain tubular graphene/alicyclic epoxy resin of a tubular graphene-alicyclic epoxy resin system. In the present invention, the tubular graphene may be selected from single-wall tube graphene (SWNT) or multi-wall tube graphene (MWNT). Wherein, SWNT are selected from manufacturers: (ii) CarbonSolution; the model is as follows: AP-SWNT (peak of particle size distribution: 1.4nm, purity: 60-90%). MWNT selection manufacturers: shenzhen nano gang ltd, model: S-MWNT-4060 (outer diameter: 40-60nm, length: <2 μm, purity: > 97%, specific surface area: 60-160 m 2/g). Preferably, the tubular graphene is AP-SWNT, and has relatively low cost and narrow particle size distribution. The source of the tubular graphene is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, graphene is used as a honeycomb-lattice two-dimensional carbon nanomaterial, has excellent mechanical properties and electricity, has important application prospects in various materials, and is considered to be one of future revolutionary materials; the multilayer sheet structures of the tubular graphene selected by the invention can form close parallel arrangement in different coating layers, different surface layers can realize a conductive path or a conductive network, the structure is favorable for improving multiple reflection loss, the specific morphology of the tubular graphene connects the conductive paths between the layers, and the tubular channel is favorable for improving the multiple reflection loss.
In the present invention, the alicyclic epoxy resin is preferably selected from one or more of methyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, and more preferably bis ((3, 4-epoxycyclohexyl) methyl) adipate. In a preferred embodiment of the present invention, the cycloaliphatic epoxy resin is bis ((3, 4-epoxycyclohexyl) methyl) adipate; the insulating material is in a saturated structure, has excellent weather resistance, does not crack or yellow, generates carbon dioxide and water during electrical decomposition, does not cause short circuit unlike graphite generated by aromatic resin, has low chlorine content, is particularly suitable for insulating materials with high requirements on electrical performance, has good high-temperature insulation property, strong arc resistance and leakage resistance, can be thermally cured and also be optically cured, is fast in curing, low in curing shrinkage rate, large in cured material crosslinking density, excellent in flexibility and good in thermal stability, and the Tg is higher than 200 ℃; therefore, bis ((3, 4-epoxycyclohexyl) methyl) adipate is preferably used as the alicyclic epoxy resin in the present invention.
The source of the alicyclic epoxy resin in the present invention is not particularly limited, and commercially available products of methyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, which are well known to those skilled in the art, may be used.
Meanwhile, the source of the organic solvent is not particularly limited in the present invention, and commercially available products of N, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC) known to those skilled in the art may be used.
In the invention, the mass ratio of the tubular graphene, the alicyclic epoxy resin and the N, N-dimethylformamide is preferably (1-3): 40: (57-59), more preferably 1: 40: 59. 2: 40: 58 or 3: 40: 57; on the basis, in the tubular graphene/alicyclic epoxy resin obtained subsequently, the mass ratio of the tubular graphene is 1-3%.
By utilizing the dynamics and thermodynamics research of high molecular resin, the resin has three different physical states under different temperature environments: glassy, high elastic (rubbery) and viscous state. The raw materials with the components with the specific content can form an alicyclic epoxy resin system containing tubular graphene, wherein the alicyclic epoxy resin is prepared by epoxidizing double bonds of alicyclic olefin, epoxy groups of the alicyclic epoxy resin are directly connected to alicyclic rings, and epoxy groups of the alicyclic epoxy resin are connected to benzene nucleus or aliphatic hydrocarbon by epoxypropyl ether; the cured product of the system after high-temperature curing has the following characteristics: (1) higher compressive and tensile strength; (2) the high-temperature-resistant rubber can still keep good mechanical property after being exposed to high temperature for a long time; (3) the arc resistance, the ultraviolet light aging resistance and the weather resistance are good.
The device for grinding treatment is not particularly limited, and a horizontal sand mill well known to those skilled in the art is adopted; the rotation speed of the grinding treatment is preferably 500rpm to 1500rpm, and more preferably 1000 rpm; the time of the grinding treatment is preferably 0.5 to 1 hour.
In the present invention, the fineness of the tubular graphene/alicyclic epoxy resin is preferably less than or equal to 20 μm.
After the tubular graphene/alicyclic epoxy resin is obtained, the obtained tubular graphene/alicyclic epoxy resin is coated on the hole wall of the honeycomb core material, and then drying treatment is carried out, so that the graphene-based wave-absorbing honeycomb is obtained.
In the present invention, the coating is preferably curtain coating, dip coating or spray coating, and more preferably curtain coating.
In the invention, the honeycomb core material is preferably an aramid paper honeycomb core material; the present invention is not particularly limited in this regard. The aramid paper honeycomb core material selected by the invention imitates a hexagonal honeycomb structure of a natural honeycomb, and is widely used as a sandwich structure core material due to light weight, high strength and high rigidity; when radar waves enter the sandwich structure from the wave-transparent surface layer, the sandwich cavity performs multiple scattering and absorption on the radar waves, so that the radar wave energy is attenuated to the maximum extent, and broadband and high-strength wave absorption effects are obtained.
In the present invention, the drying process preferably includes:
placing the coated honeycomb core material in a vacuum oven, and performing turnover deposition by taking the T direction as a central axis, wherein the rotating speed is 20-40 rpm, the temperature is 100-200 ℃, and the heat preservation time is 1-3 h;
more preferably:
and (3) placing the coated honeycomb core material in a vacuum oven, and performing turnover deposition by taking the T direction as a central axis, wherein the rotating speed is 30rpm, the temperature is 150 ℃, and the heat preservation time is 2 hours, so as to obtain the graphene-based wave-absorbing honeycomb core material. In the invention, the overturning deposition can promote the ordered arrangement of the tubular graphene on the surface layer of the substrate; meanwhile, the vacuum curing process is adopted, so that the resin system and the honeycomb base material can be fully combined, the risk of falling off of the wave absorbing layer on the inner wall is reduced, and the structural stability of the product is improved.
According to the invention, the mixed resin system containing the tubular graphene is coated on the inner wall of the honeycomb core material by adopting the conveying mode (a spray coating, dip coating or spraying mode), a layer of thin base surface is carried out, and then the combination of the tubular graphene and the base surface is realized by turning deposition, vacuum curing and other modes, so that the complexity of the working procedure is reduced, and the ordered arrangement of the tubular graphene on the surface layer of the base material is realized; the deposited surface has a plurality of bulges, most of which are tubular graphene, so that the specific surface area of the inner wall can be increased, and the electric conductivity and the heat conductivity of the material can be enhanced; in addition, the tubular graphene can play a role in supporting a framework in the material, so that the falling-off of the wave-absorbing layer on the inner wall is avoided, and the strength of the honeycomb core material is enhanced; finally, the multi-loss mechanism is introduced by depositing on the walls of the honeycomb holes, so that the wave-absorbing performance is improved, and the characteristics of light weight and high strength of the honeycomb are maintained.
The invention also provides a graphene-based wave-absorbing honeycomb which is prepared by the preparation method of the technical scheme. According to the preparation method disclosed by the technical scheme, the framework structure of the honeycomb provides high compressive strength and rigidity, and the tubular graphene distributed on the inner wall of the honeycomb hole generates a synergistic effect through electric loss, multiple scattering multiple electromagnetic wave dissipation mechanisms of the tubular graphene protrusion and the inner wall of the honeycomb, so that structural and functional integration of the light composite wave-absorbing material is realized.
The invention also provides application of the wave-absorbing honeycomb in radar stealth materials, wherein the wave-absorbing honeycomb is the graphene-based wave-absorbing honeycomb in the technical scheme. According to the invention, tubular graphene is selected as an absorbent, so that the prepared graphene-based wave-absorbing honeycomb has the effects of broadband high-efficiency absorption, light weight, high strength, strong environmental adaptability and simple processing technology as a wave-absorbing material; the projected tubular graphene can increase the specific surface area of the inner wall and enhance the conductivity and heat conductivity of the material; in addition, the tubular graphene plays a role in supporting a framework in the material, so that the falling off of the wave absorbing layer on the inner wall is avoided, and the strength of the honeycomb core material is enhanced; finally, the multi-loss mechanism is introduced by depositing on the walls of the honeycomb holes, so that the wave-absorbing performance is improved, and the light weight and high strength of the honeycomb is kept; the framework structure of the honeycomb provides high compressive strength and rigidity, and the tubular graphene distributed on the inner wall of the honeycomb hole generates a synergistic effect through electric loss, the protrusions of the tubular graphene and multiple scattering multiple electromagnetic wave dissipation mechanisms on the inner wall of the honeycomb, so that structural and functional integration of the light composite wave-absorbing material is realized, and the light composite wave-absorbing material is suitable for application in radar stealth materials.
The invention provides a graphene-based wave-absorbing honeycomb and a preparation method and application thereof; the preparation method comprises the following steps: a) mixing tubular graphene, alicyclic epoxy resin and N, N-dimethylformamide, and then grinding to obtain tubular graphene/alicyclic epoxy resin; b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb. Compared with the prior art, the preparation method provided by the invention has the advantages that the tubular graphene/alicyclic epoxy resin with specific components is coated on the hole wall of the honeycomb core material and then dried to obtain the graphene-based wave-absorbing honeycomb, the process is simple, the energy consumption is low, and the production and manufacturing period is short; the prepared graphene-based wave-absorbing honeycomb is stable in structure, good in electric conduction and heat conduction performance, light in weight, high in strength and good in wave-absorbing performance, and is suitable for being applied to radar stealth materials.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products; among them, single-walled graphene (SWNT) or multi-walled graphene (MWNT) may be optionally used. Wherein, SWNT are selected from manufacturers: carbon Solution; the model is as follows: AP-SWNT (peak of particle size distribution: 1.4nm, purity: 60-90%). MWNT selection manufacturers: shenzhen nano gang ltd, model: S-MWNT-4060 (outer diameter: 40-60nm, length: <2 μm, purity: > 97%, specific surface area: 60-160 m 2/g). Preferably, the tubular graphene is AP-SWNT, and has relatively low cost and narrow particle size distribution.
Example 1
(1) Uniformly mixing 3 wt% of tubular graphene (model: AP-SWNT), 40 wt% of bis ((3, 4-epoxycyclohexyl) methyl) adipate and 57 wt% of N, N-dimethylformamide, adding into a horizontal sand mill, and grinding at 1000rpm for 1.0h until the fineness is not more than 20 mu m to obtain the tubular graphene/alicyclic epoxy resin. Wherein 3 wt%, 40 wt% and 57 wt% are mass ratio.
(2) And (2) coating the tubular graphene/alicyclic epoxy resin obtained in the step (1) on the wall of an aramid paper honeycomb hole in a spraying conveying mode, then placing the honeycomb core material in a vacuum oven, performing turnover deposition by taking the T direction as a central axis, performing vacuum pressurization and heating to 150 ℃ at the rotating speed of 30rpm, and performing heat preservation for 2 hours to obtain the graphene-based wave-absorbing honeycomb core material (namely the graphene-based wave-absorbing honeycomb).
Example 2
(1) Uniformly mixing 2 wt% of tubular graphene (model: AP-SWNT), 40 wt% of bis ((3, 4-epoxycyclohexyl) methyl) adipate and 58 wt% of N, N-dimethylformamide, adding into a horizontal sand mill, and grinding at 1000rpm for 1.0h until the fineness is not more than 20 mu m to obtain the tubular graphene/alicyclic epoxy resin.
(2) Coating the tubular graphene/alicyclic epoxy resin obtained in the step (1) on the walls of aramid paper honeycomb holes in a spraying and coating conveying mode, placing the honeycomb core material in a vacuum oven, performing turnover deposition by taking the T direction as a central axis, performing vacuum pressurization and heating to 150 ℃, and performing heat preservation for 2 hours to obtain a graphene-based wave-absorbing honeycomb core material; the product structure is schematically shown in figure 1.
Example 3
(1) Uniformly mixing 1 wt% of tubular graphene (model: AP-SWNT), 40 wt% of bis ((3, 4-epoxycyclohexyl) methyl) adipate and 59 wt% of N, N-dimethylformamide, adding the mixture into a horizontal sand mill, and grinding at 1000rpm for 0.5h until the fineness is not more than 20 mu m to obtain the tubular graphene/alicyclic epoxy resin.
(2) And (2) coating the tubular graphene/alicyclic epoxy resin obtained in the step (1) on the walls of the aramid paper honeycomb holes in a spraying and coating conveying mode, then placing the honeycomb core material in a vacuum oven, carrying out turnover deposition by taking the T direction as a central axis, carrying out vacuum pressurization and temperature rise to 150 ℃, and carrying out heat preservation for 2 hours to obtain the graphene-based wave-absorbing honeycomb core material.
The graphene-based wave-absorbing honeycomb core material prepared by the preparation method provided by the embodiment 1-3 of the invention is subjected to various performance tests. The prepared graphene-based wave-absorbing honeycomb core material is subjected to reflectivity test through a vector network analyzer, a 300mm X5 mm metal aluminum plate is used as a standard body in the test process, and a bow-shaped frame system is adopted for reflectivity test, and the method specifically comprises the following steps:
the obtained graphene-based wave-absorbing honeycomb material plate (namely the graphene-based wave-absorbing honeycomb core material) is 300mm multiplied by 10 mm-300 mm multiplied by 20mm, the side length of a honeycomb hole is 1.83-2.75 mm, a 180mm multiplied by 5mm metal aluminum plate is used as a standard body, and a bow-shaped frame system is adopted to carry out reflectivity test on the prepared honeycomb material.
The results of the reflectance test are shown in Table 1 (wherein the sides are each 300 mm. times.300 mm).
Table 1 test results of reflectivity of graphene-based wave-absorbing honeycomb core material obtained by the preparation method provided in embodiments 1 to 3 of the present invention
As can be seen from Table 1, the reflectivity of the graphene-based wave-absorbing honeycomb core material obtained by the preparation method provided in embodiments 1-3 of the present invention is not more than-5.3 dB at 1-2GHz band, not more than-8.2 dB at 2-18GHz band, and not more than-17.2 dB at 27-40GHz band. Wherein, the testing method adopts a GJB 2038 radar wave-absorbing material reflectivity testing method.
According to the test method, the graphene-based wave-absorbing honeycomb core material obtained by the preparation method provided by the embodiment 1-3 is stable in structure, good in electric conduction and heat conduction performance, light in weight and high in strength.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a graphene-based wave-absorbing honeycomb is characterized by comprising the following steps:
a) mixing tubular graphene, alicyclic epoxy resin and an organic solvent, and then grinding to obtain tubular graphene/alicyclic epoxy resin;
b) coating the tubular graphene/alicyclic epoxy resin obtained in the step a) on the hole wall of the honeycomb core material, and drying to obtain the graphene-based wave-absorbing honeycomb.
2. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized in that: the organic solvent is one or more of N, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC).
3. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized by comprising the following steps: the tubular graphene is single-walled tubular graphene (SWNT) or multi-walled tubular graphene (MWNT).
4. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized in that: the alicyclic epoxy resin is selected from one or more of methyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate.
5. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, wherein the organic solvent is N, N-dimethylformamide, and the mass ratio of the tubular graphene, the alicyclic epoxy resin and the N, N-dimethylformamide in the step a) is (1-3): 40: (57-59).
6. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized in that: the rotation speed of the grinding treatment in the step a) is 500-1500 rpm, and the time is 0.5-1 h.
7. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized in that: the fineness of the tubular graphene/alicyclic epoxy resin in the step a) is less than or equal to 20 mu m.
8. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, characterized in that: the coating mode in the step b) is curtain coating, dip coating or spray coating.
9. The preparation method of the graphene-based wave-absorbing honeycomb according to claim 1, wherein the drying treatment in the step b) specifically comprises the following steps:
and placing the coated honeycomb core material in a vacuum oven, and performing turnover deposition by taking the T direction as a central axis, wherein the rotating speed is 20-40 rpm, the temperature is 100-200 ℃, and the heat preservation time is 1-3 h.
10. A graphene-based wave-absorbing honeycomb is characterized by being prepared by the preparation method of the graphene-based wave-absorbing honeycomb according to any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011565263.9A CN114685936A (en) | 2020-12-25 | 2020-12-25 | Graphene-based wave-absorbing honeycomb and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011565263.9A CN114685936A (en) | 2020-12-25 | 2020-12-25 | Graphene-based wave-absorbing honeycomb and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114685936A true CN114685936A (en) | 2022-07-01 |
Family
ID=82129455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011565263.9A Pending CN114685936A (en) | 2020-12-25 | 2020-12-25 | Graphene-based wave-absorbing honeycomb and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685936A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275591A (en) * | 2013-05-23 | 2013-09-04 | 浙江原邦材料科技有限公司 | 0.6-18GHz-frequency-band microwave-absorbing/epoxy anti-electromagnetic interference coating material and preparation method thereof |
| CN103600517A (en) * | 2013-11-27 | 2014-02-26 | 苏州芳磊蜂窝复合材料有限公司 | Manufacturing method of honeycomb core with nanomaterial specificity |
| CN107841123A (en) * | 2016-09-18 | 2018-03-27 | 洛阳尖端技术研究院 | A kind of three-dimensional graphite alkenyl absorbing meta-material base material and preparation method thereof |
| CN108623998A (en) * | 2017-03-23 | 2018-10-09 | 洛阳尖端技术研究院 | A kind of absorbing material and preparation method |
| CN110290689A (en) * | 2019-06-24 | 2019-09-27 | 西安安聚德纳米科技有限公司 | A kind of low frequency and wideband microwave absorbing material and preparation method thereof |
| CN112048938A (en) * | 2020-08-26 | 2020-12-08 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of wave-absorbing paper honeycomb |
-
2020
- 2020-12-25 CN CN202011565263.9A patent/CN114685936A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275591A (en) * | 2013-05-23 | 2013-09-04 | 浙江原邦材料科技有限公司 | 0.6-18GHz-frequency-band microwave-absorbing/epoxy anti-electromagnetic interference coating material and preparation method thereof |
| CN103600517A (en) * | 2013-11-27 | 2014-02-26 | 苏州芳磊蜂窝复合材料有限公司 | Manufacturing method of honeycomb core with nanomaterial specificity |
| CN107841123A (en) * | 2016-09-18 | 2018-03-27 | 洛阳尖端技术研究院 | A kind of three-dimensional graphite alkenyl absorbing meta-material base material and preparation method thereof |
| CN108623998A (en) * | 2017-03-23 | 2018-10-09 | 洛阳尖端技术研究院 | A kind of absorbing material and preparation method |
| CN110290689A (en) * | 2019-06-24 | 2019-09-27 | 西安安聚德纳米科技有限公司 | A kind of low frequency and wideband microwave absorbing material and preparation method thereof |
| CN112048938A (en) * | 2020-08-26 | 2020-12-08 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of wave-absorbing paper honeycomb |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Review on shielding mechanism and structural design of electromagnetic interference shielding composites | |
| Li et al. | Graphene oxide‐assisted multiple cross‐linking of MXene for large‐area, high‐strength, oxidation‐resistant, and multifunctional films | |
| Zhao et al. | A novel strategy in electromagnetic wave absorbing and shielding materials design: multi‐responsive field effect | |
| Wang et al. | Lightweight and robust carbon nanotube/polyimide foam for efficient and heat-resistant electromagnetic interference shielding and microwave absorption | |
| Wang et al. | Integrated multifunctional macrostructures for electromagnetic wave absorption and shielding | |
| Li et al. | Electromagnetic interference shielding of graphene aerogel with layered microstructure fabricated via mechanical compression | |
| Liang et al. | Superior electromagnetic interference shielding 3D graphene nanoplatelets/reduced graphene oxide foam/epoxy nanocomposites with high thermal conductivity | |
| Cheng et al. | Flexible and lightweight MXene/silver nanowire/polyurethane composite foam films for highly efficient electromagnetic interference shielding and photothermal conversion | |
| Zachariah et al. | Hybrid materials for electromagnetic shielding: A review | |
| Yang et al. | Flexible poly (vinylidene fluoride)-MXene/silver nanowire electromagnetic shielding films with joule heating performance | |
| Wang et al. | Marine polysaccharide-based electromagnetic absorbing/shielding materials: design principles, structure, and properties | |
| CN101289569B (en) | Method for preparing multi-wall carbon nano-tube/epoxide resin wave- absorbing and camouflage composite material | |
| Kamkar et al. | Multilayer polymeric nanocomposites for electromagnetic interference shielding: fabrication, mechanisms, and prospects | |
| Ma et al. | Hydrophobic and flame-retardant multifunctional foam for enhanced thermal insulation and broadband microwave absorption via a triple-continuous network of RGO/MWCNT-melamine composite | |
| Wang et al. | Vulcanization of Ti3C2Tx MXene/natural rubber composite films for enhanced electromagnetic interference shielding | |
| Wang et al. | Layer-by-layer assembly of low-temperature in-situ polymerized pyrrole coated nanofiber membrane for high-efficiency electromagnetic interference shielding | |
| CN102746823A (en) | Material with characteristics of fire retardation, thermal insulation and wave absorption, and preparation method thereof | |
| Wang et al. | Scalable, superelastic, and superhydrophobic MXene/silver nanowire/melamine hybrid sponges for high-performance electromagnetic interference shielding | |
| CN105658043A (en) | Electromagnetic shielding film material and preparation method thereof | |
| Liu et al. | From MXene trash to ultraflexible composites for multifunctional electromagnetic interference shielding | |
| Guo et al. | Biomass-based electromagnetic wave absorption materials with unique structures: a critical review | |
| Zhou et al. | A novel lightweight metamaterial with ultra broadband electromagnetic wave absorption induced by three-dimensional CNTs conductive-coated arrays | |
| Bi et al. | Microwave absorption and mechanical properties of CNTs/PU composites with honeycomb structure | |
| Tang et al. | Lightweight zirconium modified carbon–carbon composites with excellent microwave absorption and mechanical properties | |
| Jiang et al. | Ultralight and flexible electrospun PMIA/AgNW/Ni composite membrane with thermostability and excellent electromagnetic interference shielding effectiveness |
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 |