CN113119565A - Three-layer wave-absorbing composite material and preparation method and application thereof - Google Patents

Three-layer wave-absorbing composite material and preparation method and application thereof Download PDF

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CN113119565A
CN113119565A CN202110392760.1A CN202110392760A CN113119565A CN 113119565 A CN113119565 A CN 113119565A CN 202110392760 A CN202110392760 A CN 202110392760A CN 113119565 A CN113119565 A CN 113119565A
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graphene oxide
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白树林
刘梦佳
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Peking University
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Abstract

The invention provides a three-layer wave-absorbing composite material and a preparation method and application thereof, belonging to the technical field of electromagnetic wave-absorbing materials. Hair brushThe invention provides a three-layer wave-absorbing composite material which comprises a top layer, a middle layer and a bottom layer, wherein the top layer comprises reduced graphene oxide and thermoplastic polyolefin, and the middle layer comprises Fe3O4-reduced graphene oxide composite filler and thermoplastic polyolefin, said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The bottom layer is made of Fe and is loaded on the surface of the reduced graphene oxide3O4And thermoplastic polyolefins. The invention adopts reduced graphene oxide (rGO) and Fe3O4As a wave absorbing agent, Thermoplastic Polyolefin (TPO) is used as a matrix, wherein the TPO has remarkable waterproof performance, high elasticity and easy processing performance, the composite material with a three-layer structure is obtained, and the wave absorbing effect is improved by limiting the lamination sequence.

Description

Three-layer wave-absorbing composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electromagnetic wave absorbing materials, in particular to a three-layer wave absorbing composite material and a preparation method and application thereof.
Background
Over the past several decades, the demand for microwave absorbing materials has increased dramatically due to the increased use of commercial, scientific and military electronic equipment. Electromagnetic radiation in certain frequency bands can damage human health and interfere with the normal operation of equipment. Therefore, it is necessary to develop a material having a high electromagnetic wave absorption performance. An electromagnetic wave absorbing material excellent in performance should effectively absorb electromagnetic waves in a frequency band as wide as possible. Reflection Loss (RL) and Effective Bandwidth (EB) are two key parameters for measuring the electromagnetic wave absorption capacity of a material. RL is generally negative, with lower RL meaning that more of the incident electromagnetic wave is absorbed, and wider EB meaning that the material is able to absorb the electromagnetic wave efficiently at more frequencies. RL < -10dB, namely the material can absorb more than 90% of electromagnetic waves, is considered to be the effective absorption of the electromagnetic waves.
Materials absorb electromagnetic waves mainly through dielectric loss or magnetic loss, and magnetic loss and dielectric loss have an effect of 1+1 > 2 in combination, so that materials having both magnetic loss and dielectric loss are often used to absorb electromagnetic waves, and carbon-based materials, such as graphene, reduced graphene oxide (rGO), Carbon Nanotubes (CNTs), are often used for dielectric loss materials due to low density, suitable electrical conductivity, excellent chemical stability and thermal stability. The rGO has a small amount of functional groups, the defects caused by the functional groups can increase the absorption of the material to electromagnetic waves, and the absorption performance of the rGO is excellent in the carbon material because the rGO has certain conductivity. In the prior art, the material is composed of rGO/NiO, rGO/ZnO and rGO/Co3O4、rGO/MnO2、rGO/CoFe2O4In the wave-absorbing material composed of binary filler and other carbon-based materialsCompared with the rGO, the rGO has stronger electromagnetic wave absorption capacity. The magnetic loss material is mainly occupied by ferrite and magnetic metals such as Fe, Co, Ni, composite metals and their oxides. Fe3O4The material has excellent magnetic loss performance and is widely applied to the field of electromagnetic wave absorption.
However, the wave-absorbing material composed of the binary filler in the prior art has the problems of low wave-absorbing intensity of electromagnetic waves and narrow effective wave-absorbing frequency band.
Disclosure of Invention
In view of the above, the present invention aims to provide a three-layer wave-absorbing composite material, and a preparation method and an application thereof. The three-layer wave-absorbing composite material prepared by the invention has high wave-absorbing strength to electromagnetic waves and wide effective wave-absorbing frequency band.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a three-layer wave-absorbing composite material which comprises a top layer, a middle layer and a bottom layer, wherein the top layer is composed of reduced graphene oxide and thermoplastic polyolefin, and the middle layer is composed of Fe3O4-reduced graphene oxide composite filler and thermoplastic polyolefin, said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The bottom layer is made of Fe and is loaded on the surface of the reduced graphene oxide3O4And thermoplastic polyolefins.
Preferably, the Fe3O4-reduction of Fe in graphene oxide composite packing3O4The mass ratio of the graphene oxide to the reduced graphene oxide is 4: 1.
Preferably, the thickness of the top layer is 1.60-2.00 mm, the thickness of the middle layer is 1.10-2.00 mm, and the thickness of the bottom layer is 0.10-1.50 mm.
Preferably, the thickness of the top layer is 1.90-1.95 mm, the thickness of the middle layer is 1.30-1.85 mm, and the thickness of the bottom layer is 0.15-1.20 mm.
Preferably, the mass content of the reduced graphene oxide in the top layer is 1-5%.
Preferably, Fe in the intermediate layer3O4The mass content of the reduced graphene oxide composite filler is 5-40%.
Preferably, Fe in the bottom layer3O4The mass content of (A) is 10-50%.
Preferably, the mass content of the reduced graphene oxide in the top layer is 3%, and the mass content of Fe in the middle layer is 3%3O4-the mass content of the reduced graphene oxide composite filler is 40%, and the bottom layer contains Fe3O4The mass content of (A) is 50%.
The invention also provides a preparation method of the three-layer wave-absorbing composite material in the technical scheme, which comprises the following steps:
mixing reduced graphene oxide and thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated top plate;
mixing Fe3O4Mixing the reduced graphene oxide and ethanol, and then sequentially carrying out solid-liquid separation and drying to obtain Fe3O4-reduced graphene oxide composite filler;
subjecting said Fe to3O4-mixing the reduced graphene oxide composite filler and the thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated intermediate layer plate;
mixing Fe3O4Mixing the mixture with thermoplastic polyolefin, and then sequentially granulating and hot-press molding to obtain a prefabricated bottom plate;
and stacking the prefabricated bottom layer plate, the prefabricated middle layer plate and the prefabricated top layer plate in sequence and then performing hot press molding to obtain the three-layer wave-absorbing composite material.
The invention also provides the application of the three-layer wave-absorbing composite material in the technical scheme in electromagnetic wave absorption.
The invention provides a three-layer wave-absorbing composite material which comprises a top layer, a middle layer and a bottom layer, wherein the top layer is composed of reduced graphene oxide and thermoplastic polyolefin, and the middle layer is composed of Fe3O4-reduced graphene oxide composite filler and thermoplastic polyolefin, said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The bottom layer is made of Fe and is loaded on the surface of the reduced graphene oxide3O4And thermoplastic polyolefins. The invention adopts reduced graphene oxide (rGO) and Fe3O4As a wave absorbing agent, Thermoplastic Polyolefin (TPO) is used as a matrix, wherein the TPO has remarkable waterproof performance, high elasticity and easy processing performance, the composite material with a three-layer structure is obtained, the wave absorbing strength of electromagnetic waves is improved by limiting the lamination sequence, and meanwhile, the effective wave absorbing frequency band is widened.
Compared with a single-layer material under the same condition, the three-layer wave-absorbing composite material has better wave-absorbing performance because: (1) the three-layer wave-absorbing composite material has better impedance matching (the closer to the free space impedance 1, the better the impedance matching is), so that more electromagnetic waves can enter the material; (2) compared with a single-layer material, the three-layer wave-absorbing composite material has more interfaces due to different properties of each layer of material, when electromagnetic waves reach the interfaces of the materials of the layers, reflection loss of the electromagnetic waves at the interfaces can occur due to different impedance of each layer of material, which is also a main position of the electromagnetic waves of the three-layer wave-absorbing composite material, and the three-layer wave-absorbing composite material has more interface loss depending on the loss of the material.
Furthermore, the wave-absorbing performance of the prepared three-layer wave-absorbing composite material is greatly superior to that of the conventional mixed material by optimizing the thickness of each layer of material.
The invention also provides a preparation method of the three-layer wave-absorbing composite material in the technical scheme, and the preparation method is simple and convenient to operate and easy for industrial production.
Drawings
FIG. 1 is a graph showing the resistance values of a single layer material and a multilayer material under the same conditions;
FIG. 2 is a flow chart of the present invention for preparing three-layer wave-absorbing composite material, wherein (a) is Fe3O4A preparation process of the rGO composite filler, and (b) a preparation process of a single-layer precast slab and a three-layer wave-absorbing composite material;
FIG. 3 is Fe3O4Respectively 10%, 20%, 30%, 40%, 50% Fe3O4Reflection loss value curve of TPO;
FIG. 4 is Fe3O4-5%, 10%, 15%, 20%, 25%, 40% Fe by weight of rGO respectively3O4-reflection loss value curve of rGO/TPO;
FIG. 5 is a plot of the reflection loss values for rGO/TPO at 1%, 2%, 3%, 4%, 5% rGO by mass fraction, respectively;
FIG. 6 is a wave-absorbing performance curve of three layers of wave-absorbing composite materials with different thicknesses of each layer;
FIG. 7 shows three layers of the wave-absorbing composite material and Fe in Table 13O427 percent of Fe with the thickness of 3.00, 3.75, 3.85, 4.05, 4.15, 4.50 and 5.20 respectively3O4The wave absorbing performance curve of TPO;
FIG. 8 is a representation map of three layers of wave-absorbing composite material, top layer, bottom layer and middle layer, wherein (a) is a light-receiving mirror image of the wave-absorbing composite material, and (b) is an electron microscope image of rGO/TPO layer; (c) is Fe3O4-electron micrograph of rGO/TPO layer; (d) is Fe3O4Electron micrograph of TPO layer.
Detailed Description
The invention provides a three-layer wave-absorbing composite material which comprises a top layer, a middle layer and a bottom layer, wherein the top layer is composed of reduced graphene oxide and thermoplastic polyolefin, and the middle layer is composed of Fe3O4-reduced graphene oxide composite filler and thermoplastic polyolefin, said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The bottom layer is made of Fe and is loaded on the surface of the reduced graphene oxide3O4And thermoplastic polyolefins.
In the invention, the thickness of the top layer is preferably 1.60-2.00 mm, and more preferably 1.90-1.95 mm; the thickness of the middle layer is preferably 1.10-2.00 mm, more preferably 1.30-1.85 mm, and most preferably 1.65-1.75 mm; the thickness of the bottom layer is preferably 0.10-1.50 mm, more preferably 0.15-1.20 mm, and most preferably 0.20 mm.
In a specific embodiment of the invention, the top layer has a thickness of 1.60mm, the intermediate layer has a thickness of 1.30mm, and the bottom layer has a thickness of 0.10mm or
The thickness of the top layer is 2.00mm, the thickness of the middle layer is 1.85mm, and the thickness of the bottom layer is 0.20mm or
The thickness of the top layer is 2.00mm, the thickness of the middle layer is 1.75mm, and the thickness of the bottom layer is 0.20mm or
The thickness of the top layer is 2.00mm, the thickness of the middle layer is 2.00mm, and the thickness of the bottom layer is 0.20mm or
The thickness of the top layer is 1.90mm, the thickness of the middle layer is 1.10mm, and the thickness of the bottom layer is 1.50mm or
The thickness of the top layer is 1.95mm, the thickness of the middle layer is 1.65mm, and the thickness of the bottom layer is 0.15mm or
The thickness of top layer is 1.95mm, the thickness of intermediate level is 1.75mm, the thickness of bottom is 0.15 mm.
In the invention, the mass content of the reduced graphene oxide in the top layer is preferably 1-5%, more preferably 2-4%, and most preferably 3%.
In the present invention, the Fe3O4-reduction of Fe in graphene oxide composite packing3O4The mass ratio to reduced graphene oxide is preferably 4: 1.
In the present invention, Fe is contained in the intermediate layer3O4The mass content of the reduced graphene oxide composite filler is preferably 5-40%, more preferably 10-25%, and most preferably 15-20%.
In the present invention, the Fe3O4-reduction of Fe in graphene oxide composite packing3O4And the graphene oxide is loaded on the surface of the reduced graphene oxide.
In the present invention, Fe in the underlayer3O4The content of (b) is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and most preferably 30% by mass.
In a specific embodiment of the invention, oxygen is reduced in the top layerThe mass content of the graphene is 3%, and Fe is contained in the middle layer3O4-the mass content of the reduced graphene oxide composite filler is 40%, and the bottom layer contains Fe3O4The mass content of (A) is 50%.
The principle that the three-layer wave-absorbing composite material provided by the invention can improve the wave-absorbing performance is as follows:
according to the transmission line theory, the reflection loss value (RL) of the single-layer wave-absorbing material can be calculated according to the measured electromagnetic parameters epsilon ', epsilon', mu 'and mu' by the following formula:
Zn＝(μr/εr)1/2tanh (1)
Figure BDA0003017401620000051
εr＝ε’–jε” (3)
μr＝μ’-jμ” (4)
Znis the input impedance of the wave-absorbing material, c is the speed of light, d is the thickness of the wave-absorbing material, epsilonrAnd murRespectively the complex dielectric constant and complex permeability of the wave-absorbing material, and epsilon ', epsilon' and mu ', mu' are respectively the real part and imaginary part of the dielectric constant and the real part and imaginary part of the permeability of the wave-absorbing material. Eta0Is a characteristic impedance (eta) of free space0＝1)。
For a multilayer material with i-layer material:
Figure BDA0003017401620000061
Figure BDA0003017401620000062
Figure BDA0003017401620000063
wherein d isi，ηiAnd γiThe thickness, the inherent impedance and the propagation constant of the wave-absorbing material of the ith layer are respectively. The Reflection Loss (RL) of a multilayer material can be calculated by the following equation:
Figure BDA0003017401620000064
in order to obtain a wave-absorbing material with excellent performance, the impedance of the material needs to be matched with the impedance of a free space as much as possible. The better the impedance matching between the two, the more the incident electromagnetic wave can enter the material for absorption. After the electromagnetic parameters of the material are measured, the impedance value of the single-layer material can be calculated by the formula (1), and the impedance value of the multi-layer material can be calculated by the formula (5).
Fig. 1 shows the impedance values of the single-layer material and the multi-layer material under the same conditions, and it can be seen from fig. 1 that, for the single-layer material and the multi-layer material under the same conditions, the impedance value of the multi-layer material is closer to the impedance value of free space of 0.79, which indicates that the impedance matching between the multi-layer material and the free space is better. Under the same circumstances, the multilayer material can enable more electromagnetic waves to enter the interior of the material, while the electromagnetic waves entering the single-layer material are relatively less.
In addition, there are more interfaces in a multilayer material than in a single layer material due to the different properties of each layer material. When the electromagnetic wave reaches the interface of each layer of material, because the impedance of each layer of material is different, the electromagnetic wave is subjected to reflection loss at the interface, which is also the main position of the multilayer material for losing the electromagnetic wave. Therefore, for a single layer material, the loss of electromagnetic waves depends mainly on the properties of the material itself, such as dielectric loss and magnetic loss. Multilayer materials have more interfacial losses than the losses of the material itself.
The invention also provides a preparation method of the three-layer wave-absorbing composite material in the technical scheme, which comprises the following steps:
mixing reduced graphene oxide and thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated top plate;
mixing Fe3O4Mixing the reduced graphene oxide and ethanol, and then sequentially carrying out solid-liquid separation and drying to obtain Fe3O4-reduced graphene oxide composite filler;
subjecting said Fe to3O4-mixing the reduced graphene oxide composite filler and the thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated intermediate layer plate;
mixing Fe3O4Mixing the mixture with thermoplastic polyolefin, and then sequentially granulating and hot-press molding to obtain a prefabricated bottom plate;
and stacking the prefabricated bottom layer plate, the prefabricated middle layer plate and the prefabricated top layer plate in sequence and then performing hot press molding to obtain the three-layer wave-absorbing composite material.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art. In a specific embodiment of the present invention, the Fe3O4Purchased from Nanjing Macrode nanomaterials Inc., the reduced graphene oxide (rGO) was purchased from Cifeng graphene technology, Inc., Suzhou, and the thermoplastic polyolefin (TPO, Hifax CA 10A) was supplied by LyondellBasell.
According to the invention, reduced graphene oxide and thermoplastic polyolefin are mixed and then are subjected to granulation and hot press molding in sequence to obtain the prefabricated top plate.
The invention has no special limitation on the use amounts of the reduced graphene oxide and the thermoplastic polyolefin, and can ensure that the use amounts of the reduced graphene oxide and the thermoplastic polyolefin meet the requirements.
In the present invention, the mixing and granulating are preferably performed by a twin-screw extruder. In the invention, the extrusion temperature of the double-screw extruder is preferably 200-210 ℃.
In the invention, the pressure of the hot-press forming is preferably 1-2 MPa, and the temperature is preferably 200-210 ℃.
In the invention, Fe3O4Mixing the reduced graphene oxide and ethanol, and then sequentially carrying out solid-liquid separation and drying to obtain Fe3O4-reduced graphene oxide composite filler.
In the present invention, the Fe3O4The particle size of (A) is preferably 10 to 20 nm.
In the present invention, the Fe is preferably used3O4And respectively mixing the reduced graphene oxide and ethanol to obtain Fe3O4Dispersing liquid and reduced graphene oxide dispersing liquid, and then adding Fe3O4And (3) after the dispersion liquid is dripped into the reduced graphene oxide dispersion liquid, mixing the reduced graphene oxide dispersion liquid under stirring and ultrasonic addition to obtain a mixed suspension, and carrying out solid-liquid separation on the mixed suspension.
In the present invention, the ethanol is preferably anhydrous ethanol.
The amount of ethanol is not particularly limited in the present invention, and the Fe content can be adjusted3O4And reducing and oxidizing the graphene to be uniformly dispersed.
In the present invention, the solid-liquid separation is preferably filtration.
In the present invention, the drying is preferably freeze-drying, and specific parameters of the freeze-drying are not particularly limited in the present invention, and ethanol may be completely removed.
To obtain Fe3O4After reduction of the graphene oxide composite filler, the invention provides said Fe3O4And mixing the reduced graphene oxide composite filler and the thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain the prefabricated intermediate layer plate.
In the present invention, the specific parameters of the mixing, granulating and hot press forming are preferably the same as those in the above scheme, and are not described herein again.
In the present invention, the mass ratio of the mixed suspension to the thermoplastic polyolefin is not particularly limited, and the above-described embodiment may be satisfied.
In the invention, Fe3O4And mixing the mixture with thermoplastic polyolefin, and then sequentially granulating and hot-press forming to obtain the prefabricated bottom plate.
In the present invention for said Fe3O4The mass ratio of the thermoplastic polyolefin to the thermoplastic polyolefin is not particularly limited, and the above-mentioned embodiment may be satisfied.
In the present invention, the specific parameters of the mixing, granulating and hot press forming are preferably the same as those in the above scheme, and are not described herein again.
After the prefabricated bottom layer plate, the prefabricated middle layer plate and the prefabricated top layer plate are obtained, the prefabricated bottom layer plate, the prefabricated middle layer plate and the prefabricated top layer plate are sequentially stacked and then are subjected to hot pressing forming, and the three-layer wave-absorbing composite material is obtained.
In the present invention, the specific parameters of the hot press forming are preferably consistent with the above scheme, and are not described herein again.
The invention also provides the application of the three-layer wave-absorbing composite material in the technical scheme in the field of electromagnetic wave absorption.
In order to further illustrate the present invention, the following three-layer wave-absorbing composite material provided by the present invention, its preparation method and application are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The types and sources of the raw materials are as follows: fe3O4Powder (10-20 nm) was purchased from Nanjing Macrode nanomaterials, Inc., reduced graphene oxide (rGO) was purchased from Cifeng graphene technology, Inc., Suzhou, and thermoplastic polyolefin (TPO, Hifax CA 10A) was supplied from LyondellBasell.
Example 1
Fe3O4-preparation of rGO composite filler: as shown in FIG. 2 (a), Fe is first added3O4And the rGO powder are respectively dispersed in absolute ethyl alcohol, and the mixture is stirred and subjected to ultrasonic treatment for one hour. Then, Fe3O4Adding the dispersion liquid into the rGO dispersion liquid drop by drop, stirring and ultrasonically treating the obtained mixed suspension liquid for one hour, filtering, and freeze-drying to obtain Fe3O4-rGO composite Filler, Fe3O4Fe in-rGO composite packing3O4The mass ratio of the compound to rGO is 4: 1.
preparing a single-layer precast slab:
fe by twin screw extrusion3O4Uniformly mixing the powder and thermoplastic polyolefin, extruding at the temperature of 200 ℃, then extruding for granulation, and preparing a plate by hot-press molding at the pressure of 1MPa and the temperature of 200 ℃ to obtain Fe3O410 percent of Fe, 20 percent of Fe, 30 percent of Fe, 40 percent of Fe and 50 percent of Fe by mass fraction3O4/TPO；
Fe by twin screw extrusion3O4Uniformly mixing the-rGO composite filler and the thermoplastic polyolefin, extruding at 200 ℃, then extruding for granulation, and preparing a plate by hot press molding at 1MPa and 200 ℃ to obtain Fe3O45%, 10%, 15%, 20%, 25%, 40% Fe by weight of-rGO composite filler3O4-rGO/TPO；
The rGO and the thermoplastic polyolefin are uniformly mixed through twin-screw extrusion, the extrusion temperature is 200 ℃, then granulation is performed, and plates are prepared through hot-press molding, wherein the pressure is 1MPa, the temperature is 200 ℃, and the rGO/TPO with the rGO mass fraction of 1%, 2%, 3%, 4% and 5% is prepared.
Preparing a three-layer wave-absorbing composite material:
the single-layer material prepared in the above way is processed into Fe3O4/TPO、Fe3O4Stacking rGO/TPO and rGO/TPO for hot press forming at 200 ℃ and 1 MPa.
Fig. 2 (b) is a preparation process of a single-layer precast slab and a three-layer wave-absorbing composite material.
FIG. 3 is Fe3O4Respectively 10%, 20%, 30%, 40%, 50% Fe3O4Reflection loss value curve for/TPO, FIG. 4 is Fe3O4-5%, 10%, 15%, 20%, 25%, 40% Fe by weight of rGO respectively3O4-rGO/TPO reflection loss value curve, FIG. 5 is the reflection loss value curve for rGO/TPO with a mass fraction of 1%, 2%, 3%, 4%, 5% respectively. As shown in FIGS. 3 to 5, when Fe is added3O4Fe in TPO3O4Has the lowest reflection loss value when the mass fraction of (1) is 50%, and Fe3O4Fe in rGO/TPO3O4-the lowest reflection loss value at 40% of rGO mass fraction and the lowest reflection loss value at 3% of rGO mass fraction in rGO/TPO.
Selecting Fe3O4Fe in TPO3O4Is 50% by mass, Fe3O4Fe in rGO/TPO3O4The mass fraction of rGO is 40%, the mass fraction of rGO in rGO/TPO is 3%, the different thicknesses of the three-layer wave-absorbing composite material are researched, and the thickness data of each layer are shown in Table 1.
TABLE 1 data of different thickness of each layer of three-layer wave-absorbing composite material
Figure BDA0003017401620000101
FIG. 6 is a wave-absorbing property curve of three layers of wave-absorbing composite materials with different thicknesses, Table 2 is wave-absorbing property data of three layers of wave-absorbing composite materials with different thicknesses,
table 2 wave-absorbing performance data of three-layer wave-absorbing composite material with different thickness of each layer
Figure BDA0003017401620000102
FIG. 7 shows three layers of the wave-absorbing composite material and Fe in Table 13O427 percent of Fe with the thickness of 3.00, 3.75, 3.85, 4.05, 4.15, 4.50 and 5.20 respectively3O4The wave-absorbing strength and effective wave-absorbing bandwidth of the three-layer wave-absorbing composite material are far higher than those of a single-layer material.
FIG. 8 is a representation map of three layers of wave-absorbing composite material, top layer, bottom layer and middle layer, wherein (a) is a light-receiving mirror image of the wave-absorbing composite material, and (b) is an electron microscope image of rGO/TPO layer; (c) is Fe3O4-electron micrograph of rGO/TPO layer; (d) is Fe3O4Electron micrograph of TPO layer.
Comparative example 1
Reference is made to Zhang, H., et al, Room temperature failure of an RGO-Fe3O4RSC Advances,2014.4(28) preparation of rGO-Fe3O4A hydrogel.
Comparative example 2
Reference is made to Zong, M., et al, furniture preparation, high and microwave adsorption mechanism of RGO-Fe3O4Rsc Advances,2013.3(45) preparation of Fe3O4-rGO。
Comparative example 3
Reference is made to Cui, G., et al, Excellent Microwave Absorption Properties Derived from the Synthesis of Hollow Fe3O4@ Reduced Graphite Oxides (RGO) nanocomposites (Basel),2019.9(2)3O4@rGO。
Comparative example 4
Reference is made to Liu, Z, et al, radial design of theoretical porous Fe3O4Composites Communications,2020.22 preparation of layered porous Fe3O4/rGO。
Comparative example 5
Reference is made to The compact of Fe in Jiano, S.et al, Enhanced Microwave Absorption3O4Preparation of flake Fe and Reduced Graphene Oxide with Improved Interfacial polarization Materials,2020.22(4)3O4/rGO。
Comparative example 6
Reference is made to Wu, J., et al, The effect of GO loading on electromagnetic wave properties of Fe3O4Reduced graphene oxide Compounds International 2017.43(16): p.13146-13153 preparation of Fe3O4hybrid/rGO filler.
Comparative example 7
Reference is made to the literature Yin, Y., et al, Enhanced high-frequency absorption of anistropic Fe3O4[ graphene nanocomposites. Sci Rep,2016.6: p.25075 ] preparation of anisotropic Fe3O4/rGO。
Comparative example 8
See Zeng, X., et al, Template-Free Format of Uniform Fe3O4 HollowPreparation of hollow flower-like Fe by Nanoflower Supported on Reduced Graphene Oxide and Heat Excellent Microwave adsorption Performance (a),2018.215(7)3O4/rGO。
Table 3 shows the wave-absorbing performance data of the three-layer wave-absorbing composite material with the total thickness of 4.50 mm and 5.20mm prepared in example 1 and the composite material prepared in proportion 1-8. The three-layer wave-absorbing composite material prepared by the invention and the reported rGO and Fe3O4Compared with research work of the wave absorbing agent, the performance of the prepared material is greatly improved.
Table 3 data of wave-absorbing properties of three-layer wave-absorbing composite materials with total thicknesses of 4.50 mm and 5.20mm prepared in example 1 and composite materials prepared in proportion of 1-8
Figure BDA0003017401620000121
Figure BDA0003017401620000131
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The three-layer wave-absorbing composite material is characterized by comprising a top layer, a middle layer and a bottom layer, wherein the top layer is composed of reduced graphene oxide and thermoplastic polyolefin, and the middle layer is composed of Fe3O4-reduced graphene oxide composite filler and thermoplastic polyolefin, said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The bottom layer is made of Fe and is loaded on the surface of the reduced graphene oxide3O4And thermoplastic polyolefins.
2. The three-layer wave absorbing composite of claim 1, wherein said Fe3O4-reduction of Fe in graphene oxide composite packing3O4The mass ratio of the graphene oxide to the reduced graphene oxide is 4: 1.
3. The three-layer wave-absorbing composite material according to claim 1 or 2, wherein the thickness of the top layer is 1.60-2.00 mm, the thickness of the middle layer is 1.10-2.00 mm, and the thickness of the bottom layer is 0.10-1.50 mm.
4. The three-layer wave-absorbing composite material as claimed in claim 3, wherein the thickness of the top layer is 1.90-1.95 mm, the thickness of the middle layer is 1.30-1.85 mm, and the thickness of the bottom layer is 0.15-1.20 mm.
5. The three-layer wave-absorbing composite material according to claim 1 or 2, wherein the mass content of the reduced graphene oxide in the top layer is 1-5%.
6. Three-layer wave-absorbing composite material according to claim 1 or 2, characterized in that Fe is present in the middle layer3O4The mass content of the reduced graphene oxide composite filler is 5-40%.
7. Three-layer wave-absorbing composite material according to claim 1 or 2, characterized in that the bottom layer contains Fe3O4The mass content of (A) is 10-50%.
8. The three-layer wave-absorbing composite material of claim 1, wherein the mass content of reduced graphene oxide in the top layer is 3%, and the mass content of Fe in the middle layer is 3%3O4-the mass content of the reduced graphene oxide composite filler is 40%, and the bottom layer contains Fe3O4The mass content of (A) is 50%.
9. The preparation method of the three-layer wave-absorbing composite material of any one of claims 1 to 8, which is characterized by comprising the following steps:
mixing reduced graphene oxide and thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated top plate;
mixing Fe3O4Mixing the reduced graphene oxide and ethanol, and then sequentially carrying out solid-liquid separation and drying to obtain Fe3O4-reduced graphene oxide composite filler;
subjecting said Fe to3O4-mixing the reduced graphene oxide composite filler and the thermoplastic polyolefin, and then sequentially performing granulation and hot press molding to obtain a prefabricated intermediate layer plate;
mixing Fe3O4Mixing the mixture with thermoplastic polyolefin, and then sequentially granulating and hot-press molding to obtain a prefabricated bottom plate;
and stacking the prefabricated bottom layer plate, the prefabricated middle layer plate and the prefabricated top layer plate in sequence and then performing hot press molding to obtain the three-layer wave-absorbing composite material.
10. The use of a three layer wave absorbing composite as claimed in claim 9 in the absorption of electromagnetic waves.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114801381A (en) * 2022-03-29 2022-07-29 四川盈乐威科技有限公司 Multilayer wave-absorbing material and preparation method thereof
CN117549584A (en) * 2023-12-25 2024-02-13 武汉理工大学三亚科教创新园 Preparation method of polymer-based wave-absorbing material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173189A (en) * 2013-03-06 2013-06-26 西北工业大学 Method for preparing reduced graphene oxide/ferroferric oxide nano-grade wave-absorbing materials
CN108774390A (en) * 2018-06-22 2018-11-09 四川大学 A kind of stratiform foaming absorbing material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173189A (en) * 2013-03-06 2013-06-26 西北工业大学 Method for preparing reduced graphene oxide/ferroferric oxide nano-grade wave-absorbing materials
CN108774390A (en) * 2018-06-22 2018-11-09 四川大学 A kind of stratiform foaming absorbing material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114801381A (en) * 2022-03-29 2022-07-29 四川盈乐威科技有限公司 Multilayer wave-absorbing material and preparation method thereof
CN117549584A (en) * 2023-12-25 2024-02-13 武汉理工大学三亚科教创新园 Preparation method of polymer-based wave-absorbing material

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