CN109835010B - Wave-absorbing composite material and preparation method thereof - Google Patents
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Abstract
The invention provides a wave-absorbing composite material and a preparation method thereof, wherein a main wave-absorbing layer is clamped between an impedance matching layer and an electromagnetic loss layer to prepare the wave-absorbing composite material, the impedance matching layer and the electromagnetic loss layer are connected in a connection mode that the distance between the impedance matching layer and the electromagnetic loss layer can be regulated, and the main wave-absorbing layer three-dimensional graphene wave-absorbing material is clamped between the two layers, so that the deformation response type wave-absorbing composite material which has good wave-absorbing performance and can realize different wave-absorbing performances through self regulation is provided, the defect that the traditional wave-absorbing material only works in a single frequency band is overcome, the wave-absorbing composite material can be used for preparing the wave-absorbing material which needs to actively regulate the wave-absorbing performance, and the wave-absorbing composite material is applied to equipment with stealth requirements on different frequency bands.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a wave-absorbing composite material and a preparation method thereof.
Background
With the continuous development of high technology and the continuous popularization of high and new products, the problem of electromagnetic pollution is not limited to stealth technology in the military field, the electromagnetic pollution can also interfere precision instruments, electronic equipment and the like, even directly threatens the health of human beings, becomes a hot problem concerned by the society and the science, and as the electromagnetic pollution is more and more applied to industry and military and is gradually applied to various civil electronic and electrical equipment, electromagnetic absorption materials are highly valued by people in various fields, so that the research on the wave absorption materials for reducing the harm of electromagnetic radiation is also vital.
The basic physical principle of the wave-absorbing material is that the material can effectively absorb incident electromagnetic waves and convert the energy of the electromagnetic waves into heat energy or energy in other forms for dissipation, and the wave-absorbing material has two characteristics of impedance matching and attenuation. The working frequency band of the traditional wave-absorbing material is fixed, and the traditional wave-absorbing material generally works only in a single frequency band, so that the wave-absorbing performance of the traditional wave-absorbing material cannot be actively adjusted in use.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a wave-absorbing composite material and a preparation method thereof, and researches a wave-absorbing composite material which has good wave-absorbing performance and can actively adjust the wave-absorbing performance.
The wave-absorbing composite material provided by the invention comprises: an impedance matching layer as an upper layer; the main body wave absorbing layer is used as an intermediate layer, wherein the main body wave absorbing layer comprises a three-dimensional graphene wave absorbing material and an electromagnetic loss layer which is used as a bottom layer; the impedance matching layer is connected to the electromagnetic loss layer in a connection mode that the distance between the two layers can be regulated, and the main body wave absorbing layer is clamped between the impedance matching layer and the electromagnetic loss layer.
In the wave-absorbing composite material, the base materials of the impedance matching layer and the electromagnetic loss layer are one or a combination of more of epoxy resin, vinyl resin, quartz fiber and glass fiber.
In the wave-absorbing composite material, the absorbent of the impedance matching layer is one or a combination of more of spherical ferromagnetic metal particles and spherical ferromagnetic metal particles/dielectric composite particles.
In the wave-absorbing composite material, the spherical ferromagnetic metal particles are one or a combination of more of spherical Fe metal particles, spherical Co metal particles and spherical Ni metal particles.
In the wave-absorbing composite material, the spherical ferromagnetic metal particles/dielectric composite particles are spherical Ni/SiO2、Fe/SiO2Or Co/C.
In the wave-absorbing composite material, the absorbent of the electromagnetic loss layer is one or a combination of a plurality of sheet-shaped ferromagnetic metals and ferrites.
In the wave-absorbing composite material, the flaky ferromagnetic metal is one or a combination of more than one of flaky Fe, flaky Co and flaky Ni.
In the wave-absorbing composite material, the ferrite is ZnFe2O4、CoFe2O4、MnFe2O4One or more of the above.
The preparation method of the wave-absorbing composite material provided by the invention comprises the following steps: connecting the impedance matching layer to the electromagnetic loss layer, and simultaneously clamping the main body wave-absorbing layer between the impedance matching layer and the electromagnetic loss layer to prepare the wave-absorbing composite material, wherein the main body wave-absorbing layer comprises a three-dimensional graphene wave-absorbing material.
In the above manufacturing method, the step of manufacturing the impedance matching layer includes: dispersing an absorbent in a matrix material to prepare the impedance matching layer, wherein the matrix material of the impedance matching layer is one or more of epoxy resin, vinyl resin, quartz fiber and glass fiber, and the absorbent is one or more of spherical ferromagnetic metal particles and spherical ferromagnetic metal particle/dielectric composite particles.
In the above manufacturing method, the step of manufacturing the electromagnetic loss layer includes: dispersing an absorbent in a matrix material to prepare the electromagnetic loss layer, wherein the matrix material of the electromagnetic loss layer is one or a combination of epoxy resin, vinyl resin, quartz fiber and glass fiber, and the absorbent is one or a combination of flaky ferromagnetic metal and ferrite.
The wave-absorbing composite material is prepared by clamping the three-dimensional graphene wave-absorbing material of the main wave-absorbing layer between the impedance matching layer and the electromagnetic loss layer, the impedance matching layer and the electromagnetic loss layer are connected in a connection mode that the distance between the impedance matching layer and the electromagnetic loss layer can be regulated, the main wave-absorbing layer is clamped between the impedance matching layer and the electromagnetic loss layer, and the deformation response type wave-absorbing composite material capable of realizing different wave-absorbing performances through self regulation is prepared by utilizing the characteristic that the wave-absorbing performance of the three-dimensional graphene wave-absorbing material of the main wave-absorbing layer changes along with the change of the thickness of the three-dimensional graphene wave-absorbing material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a wave-absorbing composite material according to an embodiment of the invention, where 1 denotes an impedance matching layer, 2 denotes a main wave-absorbing layer, and 3 denotes an electromagnetic loss layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The preparation method of the wave-absorbing composite material provided by the invention comprises the following steps:
preparing a three-dimensional graphene wave-absorbing material shown as 2 in figure 1: the three-dimensional graphene wave-absorbing material is prepared by a solvothermal reduction method, firstly, a graphene oxide dispersion liquid is prepared by a modified polymers method, and the graphene oxide solution has high oxidation degree and large sheet diameter. Then diluting the solution with a solvent, adjusting the pH value of the solution to 9-11 with ammonia water to obtain a graphene solution with a certain concentration and stable dispersion, pouring the graphene solution into a hydrothermal reaction kettle for high-temperature and high-pressure solvothermal reaction, reacting at 140-180 ℃ for 16-24 hours to obtain graphene hydrogel with a three-dimensional network skeleton structure, repeatedly dialyzing and washing the graphene hydrogel with deionized water, completely removing the solvent in the graphene hydrogel, pre-freezing the graphene hydrogel in a refrigerator, drying the pre-frozen graphene hydrogel to obtain a three-dimensional graphene aerogel with certain elasticity and good mechanical properties, and annealing the three-dimensional graphene aerogel at 400-800 ℃ to obtain the three-dimensional graphene wave-absorbing material, wherein the thickness of the three-dimensional graphene wave-absorbing material is 6-10 mm. In the step, the solvent is one or more of ethylene glycol, absolute ethyl alcohol and 1-butanol, and the drying process of the graphene hydrogel comprises supercritical CO2Drying and freeze-drying or a combination of the two. The principle of the preparation process of the solvothermal reduction method is that a three-dimensional network structure is formed by self-assembly of graphene oxide micro-nano sheets based on the hydrophobic effect of the graphene oxide micro-nano sheets and pi-pi interaction, then a solvent with large surface tension in network gaps is removed through a solvent exchange process, and finally a special drying process is utilized to prepare the three-dimensional graphene material.
Preparing an impedance matching layer as shown in 1 in fig. 1: dispersing an absorbent in a matrix material to prepare the impedance matching layer, wherein the matrix material of the impedance matching layer is one or more of epoxy resin, vinyl resin, quartz fiber and glass fiberThe absorber is one or more of spherical ferromagnetic metal particles and spherical ferromagnetic metal particles/dielectric composite particles, wherein the spherical ferromagnetic metal particles are one or more of spherical Fe metal particles, spherical Co metal particles and spherical Ni metal particles, and the spherical ferromagnetic metal particles/dielectric composite particles are spherical Ni/SiO2、Fe/SiO2And one or more of Co/C, and the thickness of the impedance matching layer is 0.5-2 mm.
Preparing an electromagnetic loss layer as shown in 3 in figure 1, dispersing an absorbent in a base material to prepare the electromagnetic loss layer, wherein the base material of the electromagnetic loss layer is one or a combination of epoxy resin, vinyl resin, quartz fiber and glass fiber, the absorbent is one or a combination of sheet-shaped ferromagnetic metal and ferrite, wherein the sheet-shaped ferromagnetic metal is one or a combination of sheet-shaped Fe, Co and Ni, and the ferrite is ZnFe2O4、CoFe2O4、MnFe2O4The thickness of the electromagnetic loss layer is 0.5-2 mm.
Preparing a wave-absorbing composite material, connecting an impedance matching layer to an electromagnetic loss layer, and simultaneously clamping a main body wave-absorbing layer between the impedance matching layer and the electromagnetic loss layer to prepare the wave-absorbing composite material, wherein the main body wave-absorbing layer comprises a three-dimensional graphene wave-absorbing material. In the step, the impedance matching layer is connected to the electromagnetic loss layer through a connection mode capable of controlling the distance between the two layers, and meanwhile, the three-dimensional graphene material is clamped between the impedance matching layer and the electromagnetic loss layer, wherein the connection mode comprises one or more of bolt connection, cam connection, spring connection and electric control support.
And (3) testing the reflectivity of the wave-absorbing composite material: and testing the reflectivity of the radar absorbing material in a microwave dark room by adopting an arch method.
Example 1
Preparing a three-dimensional graphene wave-absorbing material: preparing a three-dimensional graphene wave-absorbing material by a solvothermal reduction method, firstly preparing a graphene oxide dispersion liquid by a modified polymers method, then diluting the solution by absolute ethyl alcohol, adjusting the pH value of the solution to 9 by ammonia water to obtain a graphene ethanol solution with a certain concentration and stable dispersion, pouring the graphene ethanol solution into a hydrothermal reaction kettle for solvothermal reaction at high temperature and high pressure, reacting for 24 hours at 180 ℃ to obtain graphene hydrogel with a three-dimensional network framework structure, then repeatedly dialyzing and washing the graphene hydrogel by deionized water, completely removing the absolute ethyl alcohol in the graphene hydrogel, pre-freezing in a refrigerator, freeze-drying the pre-frozen graphene hydrogel to obtain a three-dimensional graphene aerogel with ultralow density and good elasticity and mechanical property, annealing the three-dimensional graphene aerogel at 600 ℃ to obtain the three-dimensional graphene wave-absorbing material, the thickness of the three-dimensional graphene wave-absorbing material is 8 mm.
Preparing an impedance matching layer: spherical Fe metal particles were dispersed in an epoxy resin base material using a method commonly used in the art to prepare an impedance matching layer having a thickness of 1 mm.
Preparing an electromagnetic loss layer: the flaky Ni was dispersed in a vinyl resin matrix material by a method commonly used in the art to prepare an electromagnetic loss layer having a thickness of 1 mm.
The prepared impedance matching layer is connected to the prepared electromagnetic loss layer in a bolt connection mode, wherein the impedance matching layer serves as an upper layer, the electromagnetic loss layer serves as a bottom layer, and meanwhile the three-dimensional graphene wave-absorbing material is clamped between the impedance matching layer and the electromagnetic loss layer, so that the wave-absorbing composite material is prepared.
The absorption band and the corresponding reflectivity of the wave-absorbing composite material prepared by the embodiment are shown in table 1.
Comparative example 1
The thickness of the wave-absorbing composite material is compressed from 10mm to 6mm, wherein the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged, the thickness of the three-dimensional graphene is changed from 8mm to 4mm, and then the test results of the absorption wave band and the corresponding reflectivity of the wave-absorbing composite material are shown in table 1.
Example 2
Preparing a three-dimensional graphene wave-absorbing material: by passingA three-dimensional graphene wave-absorbing material is prepared by a solvothermal reduction method, firstly, graphene oxide dispersion liquid is prepared by a modified polymers method, then, absolute ethyl alcohol is used for diluting the solution, the pH value of the solution is adjusted to 11 by ammonia water, graphene ethanol solution with a certain concentration and stable dispersion is obtained, the graphene ethanol solution is poured into a hydrothermal reaction kettle for solvothermal reaction at high temperature and high pressure, graphene hydrogel with a three-dimensional network framework structure is obtained after 16 hours of reaction at 160 ℃, then, deionized water is used for repeatedly dialyzing and washing the graphene hydrogel, after the absolute ethyl alcohol in the graphene hydrogel is completely removed, pre-freezing is carried out in a refrigerator, and the pre-frozen graphene hydrogel is subjected to supercritical CO2Drying to obtain the three-dimensional graphene aerogel with ultralow density, certain elasticity and good mechanical property, and annealing the three-dimensional graphene aerogel at 600 ℃ to obtain the three-dimensional graphene wave-absorbing material, wherein the thickness of the three-dimensional graphene wave-absorbing material is 10 mm.
Preparing an impedance matching layer: spherical Co metal particles were dispersed in a vinyl resin base material by a method commonly used in the art to prepare an impedance matching layer having a thickness of 2 mm.
Preparing an electromagnetic loss layer: flaky ZnFe is prepared by adopting a method commonly used in the field2O4Dispersed in a quartz fiber base material to prepare an electromagnetic loss layer having a thickness of 1.5 mm.
The prepared impedance matching layer is connected to the prepared electromagnetic loss layer in a cam connection mode, wherein the impedance matching layer serves as an upper layer, the electromagnetic loss layer serves as a bottom layer, and meanwhile the three-dimensional graphene wave-absorbing material is clamped between the impedance matching layer and the electromagnetic loss layer, so that the wave-absorbing composite material is prepared.
The absorption band and the corresponding reflectivity of the wave-absorbing composite material prepared by the embodiment are shown in table 1.
Comparative example 2
The thickness of the wave-absorbing composite material is compressed from 13.5mm to 9.5mm, wherein the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged, the thickness of the three-dimensional graphene is changed from 10mm to 6mm, and then the test results of the absorption waveband and the corresponding reflectivity of the wave-absorbing composite material are shown in table 1.
Example 3
Preparing a three-dimensional graphene wave-absorbing material: preparing a three-dimensional graphene wave-absorbing material by a solvothermal reduction method, firstly preparing a graphene oxide dispersion liquid by a modified polymers method, then diluting the solution by ethylene glycol, adjusting the pH value of the solution to 10 by ammonia water to obtain a graphene ethanol solution with a certain concentration and stable dispersion, pouring the graphene ethanol solution into a hydrothermal reaction kettle for solvothermal reaction at high temperature and high pressure, reacting for 20 hours at 140 ℃ to obtain graphene hydrogel with a three-dimensional network framework structure, then repeatedly dialyzing and washing the graphene hydrogel by deionized water, completely removing the ethylene glycol in the graphene hydrogel, pre-freezing in a refrigerator, freeze-drying the pre-frozen graphene hydrogel to obtain a three-dimensional graphene aerogel with ultralow density and good elasticity and mechanical property, annealing the three-dimensional graphene aerogel at 600 ℃ to obtain the three-dimensional graphene wave-absorbing material, the thickness of the three-dimensional graphene wave-absorbing material is 6 mm.
Preparing an impedance matching layer: spherical Co/C was dispersed in a quartz fiber base material by a method commonly used in the art to prepare an impedance matching layer having a thickness of 0.5 mm.
Preparing an electromagnetic loss layer: flake CoFe is formed by a method commonly used in the art2O4Dispersed in a glass fiber base material to prepare an electromagnetic loss layer having a thickness of 1 mm.
The prepared impedance matching layer is connected to the prepared electromagnetic loss layer in a spring connection mode, wherein the impedance matching layer serves as an upper layer, the electromagnetic loss layer serves as a bottom layer, and meanwhile the three-dimensional graphene wave-absorbing material is clamped between the impedance matching layer and the electromagnetic loss layer, so that the wave-absorbing composite material is prepared.
The absorption band and the corresponding reflectivity of the wave-absorbing composite material prepared by the embodiment are shown in table 1.
Comparative example 3
The thickness of the wave-absorbing composite material is compressed from 7.5mm to 6.5mm, wherein the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged, the thickness of the three-dimensional graphene is changed from 6mm to 5mm, and then the test results of the absorption waveband and the corresponding reflectivity of the wave-absorbing composite material are shown in table 1.
Example 4
Preparing a three-dimensional graphene wave-absorbing material: preparing a three-dimensional graphene wave-absorbing material by a solvothermal reduction method, firstly preparing a graphene oxide dispersion liquid by a modified polymers method, then diluting the solution by ethylene glycol, adjusting the pH value of the solution to 11 by ammonia water to obtain a graphene ethanol solution with a certain concentration and stable dispersion, pouring the graphene ethanol solution into a hydrothermal reaction kettle for solvothermal reaction at high temperature and high pressure, reacting for 18 hours at 160 ℃ to obtain graphene hydrogel with a three-dimensional network framework structure, then repeatedly dialyzing and washing the graphene hydrogel by deionized water, completely removing the ethylene glycol in the graphene hydrogel, pre-freezing in a refrigerator, and performing supercritical CO (carbon monoxide) on the pre-frozen graphene hydrogel2And drying to obtain the three-dimensional graphene aerogel with ultralow density, certain elasticity and good mechanical property, and annealing the three-dimensional graphene aerogel at 400 ℃ to obtain the three-dimensional graphene wave-absorbing material, wherein the thickness of the three-dimensional graphene wave-absorbing material is 7 mm.
Preparing an impedance matching layer: the spherical Fe/SiO is prepared by the method commonly used in the field2Dispersed in an epoxy resin base material to prepare an impedance matching layer having a thickness of 1 mm.
Preparing an electromagnetic loss layer: MnFe is treated by a method commonly used in the art2O4Dispersed in an epoxy resin matrix material to prepare an electromagnetic loss layer having a thickness of 2 mm.
The prepared impedance matching layer is connected to the prepared electromagnetic loss layer in a spring connection mode, wherein the impedance matching layer serves as an upper layer, the electromagnetic loss layer serves as a bottom layer, and meanwhile the three-dimensional graphene wave-absorbing material is clamped between the impedance matching layer and the electromagnetic loss layer, so that the wave-absorbing composite material is prepared.
The absorption band and the corresponding reflectivity of the wave-absorbing composite material prepared by the embodiment are shown in table 1.
Comparative example 4
The thickness of the wave-absorbing composite material is compressed from 10mm to 8mm, wherein the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged, the thickness of the three-dimensional graphene is changed from 7mm to 5mm, and then the test results of the absorption waveband and the corresponding reflectivity of the wave-absorbing composite material are shown in table 1.
Example 5
Preparing a three-dimensional graphene wave-absorbing material: preparing a three-dimensional graphene wave-absorbing material by a solvothermal reduction method, firstly preparing a graphene oxide dispersion liquid by a modified polymers method, then diluting the solution by using 1-butanol, adjusting the pH value of the solution to 9 by using ammonia water to obtain a graphene ethanol solution with a certain concentration and stable dispersion, pouring the graphene ethanol solution into a hydrothermal reaction kettle for solvothermal reaction at high temperature and high pressure, reacting for 22 hours at 170 ℃ to obtain graphene hydrogel with a three-dimensional network framework structure, then repeatedly dialyzing and washing the graphene hydrogel by using deionized water, completely removing the 1-butanol in the graphene hydrogel, pre-freezing in a refrigerator, and performing supercritical CO (carbon monoxide) on the pre-frozen graphene hydrogel2Drying to obtain the three-dimensional graphene aerogel with ultralow density, certain elasticity and good mechanical property, and annealing the three-dimensional graphene aerogel at 800 ℃ to obtain the three-dimensional graphene wave-absorbing material, wherein the thickness of the three-dimensional graphene wave-absorbing material is 9 mm.
Preparing an impedance matching layer: spherical Ni/SiO is prepared by the method commonly used in the field2Dispersed in a glass fiber base material to prepare an impedance matching layer having a thickness of 1.5 mm.
Preparing an electromagnetic loss layer: fe is dispersed in a vinyl resin base material by a method commonly used in the art to prepare an electromagnetic loss layer having a thickness of 0.5 mm.
The prepared impedance matching layer is connected to the prepared electromagnetic loss layer in a connecting mode of the electric control support, wherein the impedance matching layer serves as an upper layer, the electromagnetic loss layer serves as a bottom layer, and meanwhile the three-dimensional graphene wave-absorbing material is clamped between the impedance matching layer and the electromagnetic loss layer, so that the wave-absorbing composite material is prepared.
The absorption band and the corresponding reflectivity of the wave-absorbing composite material prepared by the embodiment are shown in table 1.
Comparative example 5
The thickness of the wave-absorbing composite material is compressed from 11mm to 8mm, wherein the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged, the thickness of the three-dimensional graphene is changed from 9mm to 6mm, and then the test results of the absorption waveband and the corresponding reflectivity of the wave-absorbing composite material are shown in table 1.
TABLE 1 absorption band and corresponding average reflectivity of wave-absorbing composites
As can be seen from the above examples and comparative examples, when the thicknesses of the impedance matching layer and the low-frequency electromagnetic loss layer are unchanged and the thickness of the three-dimensional graphene is reduced, the radar absorption band moves towards the high-frequency direction, and the average reflectivity of the 8-18 GHz radar band can reach-20 dB. The deformation response type wave-absorbing composite material is developed by utilizing the change of the wave-absorbing performance of the three-dimensional graphene along with the change of the thickness of the three-dimensional graphene, and the performance of the composite material can be changed from strong absorption of 2-18 GHz to strong absorption of 8-18 GHz.
The invention prepares the wave-absorbing composite material by clamping the main body wave-absorbing layer between the impedance matching layer and the electromagnetic loss layer, connects the impedance matching layer and the electromagnetic loss layer by adopting a connection mode which can regulate and control the distance between the two layers, and clamps the elastic three-dimensional graphene wave-absorbing material between the two layers as the main body wave-absorbing layer.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A wave-absorbing composite, comprising:
an impedance matching layer as an upper layer;
a main body wave-absorbing layer as an intermediate layer, wherein the main body wave-absorbing layer comprises a three-dimensional graphene wave-absorbing material, and
an electromagnetic loss layer as a bottom layer;
wherein the impedance matching layer is connected to the electromagnetic loss layer in a connection manner capable of regulating the distance between the two layers, and the main body wave-absorbing layer is sandwiched between the impedance matching layer and the electromagnetic loss layer,
the thickness of the three-dimensional graphene wave-absorbing material is 6-10 mm.
2. The wave-absorbing composite material according to claim 1, wherein the matrix materials of the impedance matching layer and the electromagnetic loss layer are a combination of one or more of epoxy resin, vinyl resin, quartz fiber and glass fiber.
3. The wave absorbing composite of claim 1, wherein the absorber of the impedance matching layer is one or a combination of spherical ferromagnetic metal particles, spherical ferromagnetic metal particles/dielectric composite particles.
4. The wave-absorbing composite material according to claim 3, wherein the spherical ferromagnetic metal particles are one or more of spherical Fe metal particles, spherical Co metal particles and spherical Ni metal particles.
5. A wave-absorbing composite material according to claim 3 characterised in thatCharacterized in that the spherical ferromagnetic metal particles/dielectric composite particles are spherical Ni/SiO2、Fe/SiO2Or Co/C.
6. The wave absorbing composite of claim 1, wherein the absorber of the electromagnetic loss layer is a combination of one or more of a sheet ferromagnetic metal, a ferrite.
7. The wave absorbing composite of claim 6, wherein the sheet ferromagnetic metal is a combination of one or more of Fe, Co, Ni in sheet form.
8. The wave absorbing composite of claim 6, wherein the ferrite is ZnFe2O4、CoFe2O4、MnFe2O4One or more of the above.
9. A method for preparing the wave-absorbing composite material according to any one of claims 1 to 8, wherein an impedance matching layer is connected to an electromagnetic loss layer, and a main wave-absorbing layer is sandwiched between the impedance matching layer and the electromagnetic loss layer, so as to prepare the wave-absorbing composite material, wherein the main wave-absorbing layer comprises a three-dimensional graphene wave-absorbing material.
10. The method of manufacturing according to claim 9, wherein the step of manufacturing the impedance matching layer includes:
dispersing an absorbent in a matrix material to prepare the impedance matching layer, wherein the matrix material of the impedance matching layer is one or more of epoxy resin, vinyl resin, quartz fiber and glass fiber, and the absorbent is one or more of spherical ferromagnetic metal particles and spherical ferromagnetic metal particle/dielectric composite particles.
11. The method according to claim 9, wherein the step of preparing the electromagnetic loss layer comprises:
dispersing an absorbent in a matrix material to prepare the electromagnetic loss layer, wherein the matrix material of the electromagnetic loss layer is one or a combination of epoxy resin, vinyl resin, quartz fiber and glass fiber, and the absorbent is one or a combination of flaky ferromagnetic metal and ferrite.
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Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434134A (en) * | 2008-12-24 | 2009-05-20 | 北京化工大学 | Broadband multi-layer structured wave absorbing composite material and preparation thereof |
| CN102802395A (en) * | 2012-08-19 | 2012-11-28 | 长沙拓智金属材料科技有限责任公司 | Electromagnetic shielding composite coating resistant to information leakage and radiation pollution |
| CN103450843A (en) * | 2013-08-14 | 2013-12-18 | 安徽大学 | Preparation method of reduced graphene oxide/ferroferric oxide composite wave-absorbing hydrogel with three-dimensional structure |
| CN103740233A (en) * | 2014-01-08 | 2014-04-23 | 南京信息工程大学 | Micrometer wave absorbing coating material and preparation method thereof |
| WO2014076645A1 (en) * | 2012-11-16 | 2014-05-22 | Università Degli Studi Di Roma "La Sapienza" | Electromagnetic wave absorbing device with adjustable frequency of absorption |
| CN104099062A (en) * | 2014-07-02 | 2014-10-15 | 北京科技大学 | Compounded wave-absorbing material of grapheme/four-pin zinc oxide whisker and preparation method thereof |
| CN104608430A (en) * | 2015-01-12 | 2015-05-13 | 冯丹 | Wave-absorbing composite material |
| CN105086934A (en) * | 2014-05-06 | 2015-11-25 | 深圳光启创新技术有限公司 | Microwave absorbing composite material and preparation method therefor |
| CN105196638A (en) * | 2015-09-24 | 2015-12-30 | 北京机电工程研究所 | Broadband wave-absorbing force bearing composite material and preparing method thereof |
| CN105295959A (en) * | 2015-11-25 | 2016-02-03 | 北京旭碳新材料科技有限公司 | Composition used for flame-retardant composite material, graphene flame-retardant foam and preparation method and application thereof |
| CN105647249A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Method for preparing graphene coating through ion-induced assembly |
| CN105771895A (en) * | 2016-04-15 | 2016-07-20 | 河南科技大学 | Graphene three-dimensional composite material and preparation method and application thereof |
| CN106243379A (en) * | 2016-07-23 | 2016-12-21 | 天津大学 | A kind of electromagnetic shielding foamed composite based on graphene oxide and polymer and preparation method |
| CN106507653A (en) * | 2016-09-26 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | Adjustable polymeric conductor films of a kind of capability of electromagnetic shielding and preparation method thereof |
| CN106626619A (en) * | 2016-12-07 | 2017-05-10 | 中国航空工业集团公司北京航空材料研究院 | Microwave-absorbing composite material loaded with round patch metamaterial |
| CN106671514A (en) * | 2016-12-07 | 2017-05-17 | 中国航空工业集团公司北京航空材料研究院 | Microwave-absorbing composite material with discontinuous impedance gradient structure |
| CN106800916A (en) * | 2017-01-12 | 2017-06-06 | 东莞同济大学研究院 | A kind of graphene-based tri compound absorbing material and preparation method thereof |
| CN107072128A (en) * | 2016-12-07 | 2017-08-18 | 中国航空工业集团公司北京航空材料研究院 | Wide band electromagnetic wave absorbing material based on polyaniline graphene three-dimensional porous structure |
| CN107085340A (en) * | 2017-01-31 | 2017-08-22 | 大连理工大学 | A kind of stealthy cape of controllable three-dimensional optical based on multi-layer graphene circular layer |
| CN107399735A (en) * | 2017-08-25 | 2017-11-28 | 南京航空航天大学 | A kind of preparation method and applications of graphene composite aerogel absorbing material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10010859B2 (en) * | 2015-12-28 | 2018-07-03 | Nanotek Instruments, Inc. | Integral 3D graphene-carbon hybrid foam and devices containing same |
-
2017
- 2017-11-29 CN CN201711228998.0A patent/CN109835010B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434134A (en) * | 2008-12-24 | 2009-05-20 | 北京化工大学 | Broadband multi-layer structured wave absorbing composite material and preparation thereof |
| CN102802395A (en) * | 2012-08-19 | 2012-11-28 | 长沙拓智金属材料科技有限责任公司 | Electromagnetic shielding composite coating resistant to information leakage and radiation pollution |
| WO2014076645A1 (en) * | 2012-11-16 | 2014-05-22 | Università Degli Studi Di Roma "La Sapienza" | Electromagnetic wave absorbing device with adjustable frequency of absorption |
| CN103450843A (en) * | 2013-08-14 | 2013-12-18 | 安徽大学 | Preparation method of reduced graphene oxide/ferroferric oxide composite wave-absorbing hydrogel with three-dimensional structure |
| CN103740233A (en) * | 2014-01-08 | 2014-04-23 | 南京信息工程大学 | Micrometer wave absorbing coating material and preparation method thereof |
| CN105086934A (en) * | 2014-05-06 | 2015-11-25 | 深圳光启创新技术有限公司 | Microwave absorbing composite material and preparation method therefor |
| CN104099062A (en) * | 2014-07-02 | 2014-10-15 | 北京科技大学 | Compounded wave-absorbing material of grapheme/four-pin zinc oxide whisker and preparation method thereof |
| CN104608430A (en) * | 2015-01-12 | 2015-05-13 | 冯丹 | Wave-absorbing composite material |
| CN105196638A (en) * | 2015-09-24 | 2015-12-30 | 北京机电工程研究所 | Broadband wave-absorbing force bearing composite material and preparing method thereof |
| CN105295959A (en) * | 2015-11-25 | 2016-02-03 | 北京旭碳新材料科技有限公司 | Composition used for flame-retardant composite material, graphene flame-retardant foam and preparation method and application thereof |
| CN105647249A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Method for preparing graphene coating through ion-induced assembly |
| CN105771895A (en) * | 2016-04-15 | 2016-07-20 | 河南科技大学 | Graphene three-dimensional composite material and preparation method and application thereof |
| CN106243379A (en) * | 2016-07-23 | 2016-12-21 | 天津大学 | A kind of electromagnetic shielding foamed composite based on graphene oxide and polymer and preparation method |
| CN106507653A (en) * | 2016-09-26 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | Adjustable polymeric conductor films of a kind of capability of electromagnetic shielding and preparation method thereof |
| CN106626619A (en) * | 2016-12-07 | 2017-05-10 | 中国航空工业集团公司北京航空材料研究院 | Microwave-absorbing composite material loaded with round patch metamaterial |
| CN106671514A (en) * | 2016-12-07 | 2017-05-17 | 中国航空工业集团公司北京航空材料研究院 | Microwave-absorbing composite material with discontinuous impedance gradient structure |
| CN107072128A (en) * | 2016-12-07 | 2017-08-18 | 中国航空工业集团公司北京航空材料研究院 | Wide band electromagnetic wave absorbing material based on polyaniline graphene three-dimensional porous structure |
| CN106800916A (en) * | 2017-01-12 | 2017-06-06 | 东莞同济大学研究院 | A kind of graphene-based tri compound absorbing material and preparation method thereof |
| CN107085340A (en) * | 2017-01-31 | 2017-08-22 | 大连理工大学 | A kind of stealthy cape of controllable three-dimensional optical based on multi-layer graphene circular layer |
| CN107399735A (en) * | 2017-08-25 | 2017-11-28 | 南京航空航天大学 | A kind of preparation method and applications of graphene composite aerogel absorbing material |
Non-Patent Citations (1)
| Title |
|---|
| 复合材料多层结构设计及吸波性能研究;崔晓冬 等;《功能材料》;20060731;第37卷;第1069-1072页 * |
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