CN105524466A - Porous graphene electromagnetic wave absorbing composite material, preparation method and applications thereof - Google Patents
Porous graphene electromagnetic wave absorbing composite material, preparation method and applications thereof Download PDFInfo
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- CN105524466A CN105524466A CN201410505682.1A CN201410505682A CN105524466A CN 105524466 A CN105524466 A CN 105524466A CN 201410505682 A CN201410505682 A CN 201410505682A CN 105524466 A CN105524466 A CN 105524466A
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- composite material
- electromagnetic wave
- porous graphene
- wave absorption
- absorption composite
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Abstract
The present invention discloses a porous graphene electromagnetic wave absorbing composite material, a preparation method and applications thereof. The composite material is formed by mainly compounding Fe<3+> graphene micro-sheet, a polymer and a foaming agent, and has a porous structure, wherein the pore size of the pore channels in the porous structure is 1 nm-1 cm, and the porosity is 50-90%. The preparation method comprises: uniformly mixing the Fe<3+> graphene micro-sheet, the polymer and the foaming agent, and carrying out heating foaming to obtain the composite material. According to the present invention, the porous graphene electromagnetic wave absorbing composite material has advantages of light weight, high porosity, wide absorption frequency band, corrosion resistance, high temperature resistance and the like, can achieve important applications in electromagnetic shielding and electromagnetic stealth, and can further be widely used in sound insulation coating materials, heat dissipating coating materials, adsorption carriers and other fields, and the preparation method has characteristics of simple process, low cost and easy industrial production.
Description
Technical field
The present invention relates to a kind of electromagnetic wave shielding, absorbing material and preparation technology thereof, particularly a kind of porous graphene electromagnetic wave absorption composite material, its preparation method and application, belong to nano material sciemtifec and technical sphere.
Background technology
The development of electronic information technology and the universal of electronic product, make hertzian wave extensively exist in people's daily life.The thorny problem such as electromagenetic wave radiation causes electromagnetic pollution, electromagnetic interference, divulge a secret, hampers electronic information industrial development.The scheme effectively addressed this problem develops to absorb the electromagnetic material of special frequency channel.Therefore, absorbing material is with a wide range of applications in civil field, household electrical appliance ubiquity electromagnetic radiation, also effectively can be suppressed, can also be used to the exposure suit etc. being pregnant woman by reasonable employment absorbing material and components and parts thereof.Meanwhile, absorbing material can be widely used in stealthy technique.At various weaponry and military installations applied atop absorbing materials such as aircraft, guided missile, tank, naval vessels, warehouses, just can absorb and scout electric wave, reflection attenuation signal, thus break through the defence area of enemy radar, this is a kind of powerful measure of counterradar reconnaissance, reduces a kind of method that weapons system are attacked by infrared guidance guided missile and laser weapon.In addition, electromagnetic wave absorbent material also can be used to the equipment such as swab handle support and breather line of the air base navigational aids such as hidden landing headlight and other uphole equipment, ship mast, deck, submarine.Also it can be utilized to carry out the equipment such as safeguard protection High power radar, communication equipment, microwave heating, prevent electromagnetic radiation or leakage, protection operator healthy.Also can be used as wallcovering, absorb the electromagnetic radiation that household electrical appliance send.In addition, except requiring that absorbing material is having hertzian wave except high specific absorption in broad frequency band on engineer applied, also require that material has light weight, heatproof, moisture-proof and the performance such as anticorrosive.But existing absorbing material is all difficult to meet these performance requirements simultaneously.
Summary of the invention
For the deficiencies in the prior art, main purpose of the present invention is to provide a kind of porous graphene electromagnetic wave absorption composite material and preparation method thereof.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
A kind of porous graphene electromagnetic wave absorption composite material, primarily of containing Fe
3+graphene microchip, polymkeric substance and whipping agent be compounded to form, and there is vesicular structure, in described vesicular structure, the aperture in duct is 1nm-1cm, and porosity is 50%-90%.
Wherein, in described vesicular structure, the aperture in duct is preferably 100nm-100 μm, is especially preferably 10 μm-70 μm.
Wherein, the porosity of described vesicular structure is preferably 70%-90%, is especially preferably 85%-90%.
Further, the density of described porous graphene electromagnetic wave absorption composite material is 0.1g/cm
3-50g/cm
3, resistance to corrosion is strong, and ageing resistance is good, and specific conductivity can be: 10S/cm-400S/cm.(fly senior apprentice mutually, give a scope), thermal conductivity exists: 0.5W/ (mK)-15W/ (mK).
Further, described porous graphene electromagnetic wave absorption composite material is that the electromagnetic specific absorption of 8GHz-13GHz is at 10%-60% for wavelength.
Further, described containing Fe
3+the thickness of graphene microchip be preferably 0.34nm ~ 1mm, radial dimension is preferably 1
μm ~ 1000
μm.
Further, described containing Fe
3+the Fe of graphene microchip
3+content be 0.1wt% ~ 90wt%, be preferably 0.5wt% ~ 50wt%, be especially preferably 1wt% ~ 20wt%.
Further, described containing Fe
3+graphene microchip can be utilize FeCl
3deng the grapheme material prepared as intercalator, wherein Fe
3+content can control by controlling the means such as the addition of iron(ic) chloride and washing.
Further, described porous graphene electromagnetic wave absorption composite material can be powder or lumphy structure, can certainly be scattered in solvent formed liquid.
Wherein, when for lumphy structure, the specific surface area of described porous graphene electromagnetic wave absorption composite material is preferably 100 ~ 900m
2/ g, is especially preferably 700 ~ 900m
2/ g.
Further, described whipping agent with containing Fe
3+the mass ratio of graphene microchip be preferably 1/1000 ~ 1/0.1, be especially preferably 1/100 ~ 1/10.
Further, described containing Fe
3+graphene microchip and the mass ratio of polymkeric substance be 1/1000 ~ 995/1, be especially preferably 1/10 ~ 2/1.
Wherein, described polymkeric substance can be selected from but be not limited to polymkeric substance or its mixtures such as polyaniline, polypyrrole, Polythiophene, epoxy resin, silicon rubber, polyethylene, polypropylene, polyvinyl chloride, high density polyethylene(HDPE), polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, resol, polymethylmethacrylate, polymeric amide, rubber resin, polyoxyethylene glycol, polycarbonate, polyimide, nylon.
Wherein, described whipping agent can be carbonate (such as Na
2cO
3, K
2cO
3), H
2o
2, N, N '-dinitrosopentamethlyene tetramine (DPT), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (ADC), Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, two azoaminobenzenes, Barium azodicarboxylate, 4,4 '-disulfonyl hydrazide diphenyl ether (OBSH), to benzol sulfohydrazide, 3,3 '-disulfonyl hydrazide sulfobenzide, 4,4 '-two benzene disulfohydrazide, 1,3-benzene disulfohydrazide, Isosorbide-5-Nitrae-benzene disulfohydrazide etc. or its mixture.
The preparation method of any one porous graphene electromagnetic wave absorption composite material aforementioned, comprising: will containing Fe
3+graphene microchip, after polymkeric substance and/or polymer monomer and whipping agent Homogeneous phase mixing, foamable, obtains described matrix material; Wherein the processing condition of foamable comprise: Heating temperature is preferably 10 DEG C-150 DEG C, and the time is preferably 1-5h.
Wherein, described containing Fe for making
3+graphene microchip, polymkeric substance and/or polymer monomer and whipping agent Homogeneous phase mixing, wherein a kind of feasible mode is, will containing Fe
3+graphene microchip, polymkeric substance and whipping agent stir, stirring velocity is 100-400rpm/min.
Present invention also offers any one porous graphene electromagnetic wave absorption composite material aforementioned in preparing in sound-proof material or device, heat sink material or device, adsorption carrier material or device, electromagnetic shielding material or device, electromagnetism stealth material or device and electromagnetic-wave absorbent or device any one purposes.
The present invention selects containing Fe
+ 3graphene microchip as raw material, through reduction after can obtain Fe
3o
4, thus make the matrix material of formation have higher specific conductivity and magnetic permeability.And by regulating Fe
+ 3content and the ratio of graphene microchip and polymkeric substance, the specific conductivity of matrix material and magnetic permeability can be made as far as possible close, thus make matrix material have good electrical magnetic absorption effect, wherein, adoptable regulating measure is various, control method flexibly, simple.Postscript, because iron in graphene microchip is with Fe
+ 3form occur, therefore can be implemented in being uniformly distributed in matrix material.Further, by adding whipping agent, matrix material being made vesicular, the absorption of electromagnetic wave efficiency of matrix material can be improved by re-absorption effect.
Compared with prior art, advantage of the present invention comprises: this porous graphene electromagnetic wave absorption composite material has the advantages such as quality is light, hole is many, absorption band is wide, corrosion-resistant, high temperature resistant, important application can be obtained in electromagnetic shielding and electromagnetism stealth, also the different field such as deadener, heat radiation coating, absorption carrier can be widely used in, and its preparation technology is simple, with low cost, be easy to suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is containing Fe in embodiment 1-2
3+graphene microchip AFM figure;
Fig. 2 is the SEM figure of porous graphene Wave suction composite material in embodiment 1;
Fig. 3 is the uptake factor (A) of porous graphene Wave suction composite material in embodiment 1, reflection coefficient (R) and transmissivity (T) curve.
Specific embodiments
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be described in detail the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
In order to illustrate technical scheme of the present invention further, be described below in conjunction with example.
embodiment 1
Get the Graphene of 1g containing iron ion (that is, containing Fe
3+graphene microchip, it can be utilize FeCl
3grapheme material prepared by intercalation) join in 50ml silicon rubber, then add 0.5g hydrogen peroxide, at room temperature magnetic agitation 5 minutes, stirring velocity is 400r/min, and reheat to 80 DEG C of solidifications 12 hours, namely cooling obtains porous graphene matrix material.The density of gained matrix material is 5g/cm
3, specific conductivity is 50S/cm, and thermal conductivity is: 5W/ (mK), and has anti-oxidant, anticorrosive, the performances such as acid and alkali-resistance.
The SEM figure of this porous graphene matrix material and uptake factor, reflection coefficient and transmissivity curve please consult Fig. 2 and Fig. 3 respectively.
embodiment 2
Get 1g to join in 50ml polyaniline containing the Graphene of iron ion, add 0.5g4,4 '-two benzene disulfohydrazide, at room temperature magnetic agitation 10 minutes, rotating speed 300r/min, be heated to 100 DEG C of solidifications 8 hours, namely cooling obtains porous graphene matrix material.The density of gained matrix material is 1g/cm
3, specific conductivity is 30S/cm, and thermal conductivity is: 4.5W/ (mK), and has anti-oxidant, anticorrosive, the performances such as acid and alkali-resistance.
Compared to existing electromagnetic wave absorption composite material, the present invention can regulate specific conductivity and the magnetic permeability of matrix material by multiple means, and Fe
3o
4be evenly distributed in the composite; And this matrix material porous nickel, on the basis with high electromagnetic wave absorption performance, also has good heat conductivility simultaneously.
It should be noted that, in this article, when not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a porous graphene electromagnetic wave absorption composite material, is characterized in that it is primarily of containing Fe
3+graphene microchip, polymkeric substance and whipping agent be compounded to form, and there is vesicular structure, in described vesicular structure, the aperture in duct is 1nm-1cm, and porosity is 50%-90%.
2. porous graphene electromagnetic wave absorption composite material according to claim 1, is characterized in that described porous graphene electromagnetic wave absorption composite material is 10% ~ 60% for the electromagnetic specific absorption that wavelength is 8GHz-13GHz.
3. porous graphene electromagnetic wave absorption composite material according to claim 1, is characterized in that described containing Fe
3+the thickness of graphene microchip be 0.34nm ~ 1mm, radial dimension is 1
μm ~ 1000
μm.
4. the porous graphene electromagnetic wave absorption composite material according to claim 1 or 3, is characterized in that described containing Fe
3+the Fe of graphene microchip
3+content be 0.1wt% ~ 90wt%.
5. the porous graphene electromagnetic wave absorption composite material according to any one of claim 1-3, it is characterized in that it is powder or lumphy structure, and the specific surface area of lumphy structure is 100 ~ 900m
2/ g.
6. the porous graphene electromagnetic wave absorption composite material according to any one of claim 1-3, is characterized in that described whipping agent and contains Fe
3+the mass ratio of graphene microchip be 1/1000 ~ 1/0.1, and described containing Fe
3+graphene microchip and the mass ratio of polymkeric substance be 1/1000 ~ 995/1.
7. the porous graphene electromagnetic wave absorption composite material according to any one of claim 1-3, is characterized in that described polymkeric substance comprises the combination of any one or more in polyaniline, polypyrrole, Polythiophene, epoxy resin, silicon rubber, polyethylene, polypropylene, polyvinyl chloride, high density polyethylene(HDPE), polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, resol, polymethylmethacrylate, polymeric amide, rubber resin, polyoxyethylene glycol, polycarbonate, polyimide, nylon.
8. the porous graphene electromagnetic wave absorption composite material according to any one of claim 1-3, is characterized in that described whipping agent comprises carbonate, H
2o
2, N, N '-dinitrosopentamethlyene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, two azoaminobenzenes, Barium azodicarboxylate, 4,4 '-disulfonyl hydrazide diphenyl ether, to benzol sulfohydrazide, 3,3 '-disulfonyl hydrazide sulfobenzide, 4,4 '-two benzene disulfohydrazide, 1, the combination of any one or more in 3-benzene disulfohydrazide, Isosorbide-5-Nitrae-benzene disulfohydrazide.
9. the preparation method of porous graphene electromagnetic wave absorption composite material according to any one of claim 1-8, is characterized in that comprising: will containing Fe
3+graphene microchip, after polymkeric substance and/or polymer monomer and whipping agent Homogeneous phase mixing, foamable, obtains described matrix material; Wherein the processing condition of foamable comprise: Heating temperature is 10 DEG C-150 DEG C, and the time is 1-5h.
10. porous graphene electromagnetic wave absorption composite material according to any one of claim 1-9 is in preparing in sound-proof material or device, heat sink material or device, adsorption carrier material or device, electromagnetic shielding material or device, electromagnetism stealth material or device and electromagnetic-wave absorbent or device any one purposes.
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| CN105670456A (en) * | 2016-01-28 | 2016-06-15 | 赵文立 | Material capable of shielding electromagnetic waves caused by groundwater |
| CN106564227A (en) * | 2016-10-21 | 2017-04-19 | 中国科学院宁波材料技术与工程研究所 | Polymer/graphene foamed material with electromagnetic shielding performance, and preparation method and application thereof |
| CN107253708A (en) * | 2017-04-29 | 2017-10-17 | 成都博美实润科技有限公司 | A kind of preparation method for the phenolic resin base porous carbon being modified based on graphene |
| CN107603131A (en) * | 2017-10-20 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of low energy consumption, the method for prepare with scale graphene filling master batch |
| CN107903394A (en) * | 2017-11-16 | 2018-04-13 | 厦门大学 | The synthetic method of high polymer/graphene@magnetic nano-particle foamed composites |
| CN108841158A (en) * | 2018-06-30 | 2018-11-20 | 杭州高烯科技有限公司 | A kind of graphene-foaming polycarbonate composite material and preparation method thereof |
| CN109054242A (en) * | 2018-07-19 | 2018-12-21 | 皖西学院 | Porous graphene electromagnetic wave absorption composite material, preparation method and application |
| CN110564088A (en) * | 2019-08-26 | 2019-12-13 | 兰州理工大学 | self-healing graphene stealth film and preparation method thereof |
| CN113636540A (en) * | 2021-07-28 | 2021-11-12 | 五邑大学 | Sound absorption material and preparation method and application thereof |
| CN113929963A (en) * | 2021-11-16 | 2022-01-14 | 深圳市博恩实业有限公司 | Heat-conducting wave-absorbing sheet and preparation method thereof |
| CN114752101A (en) * | 2022-04-25 | 2022-07-15 | 南京航空航天大学 | Fe3O4Preparation method of/rGO/polyimide aerogel electromagnetic wave-absorbing material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670456A (en) * | 2016-01-28 | 2016-06-15 | 赵文立 | Material capable of shielding electromagnetic waves caused by groundwater |
| CN106564227A (en) * | 2016-10-21 | 2017-04-19 | 中国科学院宁波材料技术与工程研究所 | Polymer/graphene foamed material with electromagnetic shielding performance, and preparation method and application thereof |
| CN107253708A (en) * | 2017-04-29 | 2017-10-17 | 成都博美实润科技有限公司 | A kind of preparation method for the phenolic resin base porous carbon being modified based on graphene |
| CN107603131A (en) * | 2017-10-20 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of low energy consumption, the method for prepare with scale graphene filling master batch |
| CN107603131B (en) * | 2017-10-20 | 2021-03-02 | 成都新柯力化工科技有限公司 | Low-energy-consumption large-scale preparation method of graphene filling master batch |
| CN107903394A (en) * | 2017-11-16 | 2018-04-13 | 厦门大学 | The synthetic method of high polymer/graphene@magnetic nano-particle foamed composites |
| CN108841158A (en) * | 2018-06-30 | 2018-11-20 | 杭州高烯科技有限公司 | A kind of graphene-foaming polycarbonate composite material and preparation method thereof |
| CN109054242A (en) * | 2018-07-19 | 2018-12-21 | 皖西学院 | Porous graphene electromagnetic wave absorption composite material, preparation method and application |
| CN110564088A (en) * | 2019-08-26 | 2019-12-13 | 兰州理工大学 | self-healing graphene stealth film and preparation method thereof |
| CN113636540A (en) * | 2021-07-28 | 2021-11-12 | 五邑大学 | Sound absorption material and preparation method and application thereof |
| CN113929963A (en) * | 2021-11-16 | 2022-01-14 | 深圳市博恩实业有限公司 | Heat-conducting wave-absorbing sheet and preparation method thereof |
| CN114752101A (en) * | 2022-04-25 | 2022-07-15 | 南京航空航天大学 | Fe3O4Preparation method of/rGO/polyimide aerogel electromagnetic wave-absorbing material |
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Application publication date: 20160427 |