CN114531837B - Wave-absorbing material with composite structure and preparation method thereof - Google Patents
Wave-absorbing material with composite structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a wave-absorbing material with a composite structure, which comprises a high-frequency rare earth soft magnetic layer adsorbed on a substrate, a FeSiAl layer formed on the high-frequency rare earth soft magnetic layer and a carbonyl iron layer formed on the FeSiAl layer, wherein the mass ratio of the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carbonyl iron layer in the wave-absorbing material is in gradient change. The wave-absorbing material has higher broadband wave-absorbing performance and magnetoelectric characteristics. The invention also provides a preparation method of the wave-absorbing material with the composite structure, and the preparation method is simple and efficient.
Description
Technical Field
The invention belongs to the field of wave-absorbing materials, and particularly relates to a wave-absorbing material with a composite structure and a preparation method thereof.
Background
It is well known that wave absorbing materials can convert electromagnetic wave energy into other forms of energy or through interference cancellation of electromagnetic waves, thereby solving the problems of electromagnetic pollution and stealth of aircraft. In recent years, wave absorbing materials play an important role in the fields of military 'stealth' technology, improvement of electromagnetic compatibility, prevention of electromagnetic radiation, prevention of information leakage and the like. For a wave-absorbing material, the material quality, impedance matching, magnetic loss capability, the frequency range capable of absorbing electromagnetic waves and the like are key factors for measuring the performance of the wave-absorbing material.
The wave absorbing material converts electromagnetic energy of incident electromagnetic waves into heat energy through a self loss mechanism to dissipate the heat energy, or reduces echo of the incident electromagnetic waves due to interference, so that the electromagnetic energy is dispersed in other directions.
Magnetic wave absorbing materials are the most studied and used class at present. In general, magnetic wave absorbing materials have important strategic positions in the current army and civil defense field due to high temperature stability, easy processing and broadband high efficiency. How to effectively arrange different magnetic materials so as to widen the wave absorption frequency band and enhance the wave absorption characteristics is always a research hot spot in the field.
The Chinese patent application No. 200810075570.1 discloses a multilayer radar wave-absorbing coating and a preparation method thereof, wherein the wave-absorbing coating comprises dielectric loss composite coating layers and magnetic loss composite coating layers which are alternately overlapped. Wherein the dielectric loss coating mainly comprises tetrapod-like zinc oxide whiskers and conductive carbon black; the magnetic loss composite coating mainly comprises ferroferric oxide and nano iron powder; the coating method is applied to the aluminum flat plate material by spraying or brushing, and the spraying sequence from the bottom layer to the surface layer is as follows: the reflectivity of the magnetic layer, the dielectric layer and the magnetic-dielectric layer in the wave band of 4-8 GHz reaches-4 to-6 dB; the reflectivity in the 8-18 GHz wave band reaches-5 to-8 dB.
The Chinese patent application No. 201910428518.8 discloses a high-temperature-resistant radar absorbing material with a multilayer structure, which sequentially comprises an inner dielectric layer, a high-temperature-resistant dielectric coating and an outer dielectric layer from inside to outside, wherein the high-temperature-resistant dielectric coating is Al-doped Ti 3 SiC 2 A ceramic dielectric coating; the medium layer is made of superfine glass fiber reinforced oxide matrix composite material. It has a frequency of 8.2-12.4 GHzThe microwave loss performance of the material is greatly improved within the range of the rate.
In summary, it can be seen that in the research on broadband wave-absorbing materials in the disclosed technology, the wave-absorbing frequency band and the effect are not satisfactory all the time, and the requirements are not met. In order to realize high efficiency and thin layer of the broadband wave-absorbing material, the field is required to develop a novel composite wave-absorbing material with excellent magnetoelectric characteristics and broadband microwave absorption characteristics.
Disclosure of Invention
The invention provides a wave-absorbing material with a composite structure, which has higher broadband wave-absorbing performance and magnetoelectric characteristics.
The wave absorbing material with the composite structure comprises a high-frequency rare earth soft magnetic layer adsorbed on a substrate, a FeSiAl layer formed on the high-frequency rare earth soft magnetic layer and a carbonyl iron layer formed on the FeSiAl layer, wherein the mass ratio of the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carbonyl iron layer to the wave absorbing material is in gradient change.
Considering the complementarity of magneto-electric characteristics of carbonyl iron, feSiAl layers and high-frequency rare earth soft magnetic in a microwave frequency band (dielectric constant is sequentially increased, magnetic permeability is sequentially increased and the action frequency point of microwave loss capability is gradually increased), the invention optimizes the impedance between the composite wave-absorbing material layer and the interlayer through the electromagnetic coupling and the synergistic effect of the three layers, namely the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carbonyl iron layer, widens the broadband frequency band coverage capability of the material, and finally improves the broadband wave-absorbing characteristic of the material.
The mass ratio of the high-frequency rare earth soft magnetic layer to the FeSiAl layer to the carboxyl iron layer in the wave-absorbing material is 60-80:20-15:10-5 respectively. This duty cycle is considered mainly from the following two points: (1) The binding force between the metal substrate and the composite coating is improved, and the rare earth soft magnetic display sheet layer is suitable to be used as a contact layer of the metal substrate; however, too high a rare earth soft magnetic layer thickness can result in a decrease in the binding force of the metal substrate and the coating, which is unfavorable for repeated use in severe environments; (2) Considering the strong absorption and high permeability characteristics of the high-frequency rare earth soft magnetic layer, the rare earth soft magnetic layer with relatively high thickness is beneficial to reducing the total coating thickness, and the purpose of strong absorption of a thin layer is achieved.
The thickness of the wave-absorbing material with the composite structure is 0.8-3.0 mm.
The thicknesses of the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carboxyl iron layer are respectively 0.5-1.5:0.2-0.7:0.1-0.8mm.
The chemical formula of the high-frequency rare earth soft magnetic is A a Co b Fe c Wherein A is one of Y, pr, nd, er, gd, tb, dy, ho rare earth elements, and A a Co b Wherein the content of A atoms is 30-35%, the content of Co atoms is 25-35%, and the content of Fe atoms is 30-45%.
The strong absorption and high permeability of the high-frequency rare earth soft magnetic layer make the high-frequency rare earth soft magnetic layer become key for wide-frequency expansion, the bonding effect between layers is the bonding force of epoxy resin used in 3D printing, thin epoxy resin exists between layers, and the curing at high temperature presents a certain bonding force, thereby meeting the use requirement
The broadband wave absorbing performance of the wave absorbing material with the composite structure is that the maximum reflectivity is-30 to-45 dB, and the coverage width of an effective frequency band is 4-6.5GHz
The invention also discloses a preparation method of the wave-absorbing material with the composite structure, which comprises the following steps:
(1) Mixing the high-frequency rare earth soft magnet, the solvent and the 3D printing liquid to obtain a mixed solution A, mixing the FeSiAl, the solvent and the 3D printing liquid to obtain a mixed solution B, and mixing the carbonyl iron powder, the solvent and the 3D printing liquid to obtain a mixed solution C;
(2) Printing the mixed solution A on the surface of a substrate to form a high-frequency rare earth soft magnetic layer by a 3D printing technology, printing the mixed solution B on the surface of the high-frequency rare earth soft magnetic layer to obtain a high-frequency rare earth soft magnetic layer/FeSiAl layer, printing the mixed solution C on the surface of the FeSiAl layer to obtain the high-frequency rare earth soft magnetic layer/FeSiAl layer/carbonyl iron layer, and curing to obtain the wave-absorbing material with the composite structure.
The solvent is one or more of acetone, n-hexane, cyclohexanone, butylbenzene, dimethylbenzene and isobutanol.
The curing process is to cure for 1-2 hours at 100-300 ℃.
The invention principle of the invention is as follows: because the single-layer wave-absorbing material is difficult to achieve the ideal effect, a plurality of wave-absorbing materials are often used for superposition to form the wave-absorbing body with the multi-layer structure. The electromagnetic compatibility band and bandwidth required for the multilayered absorber can be realized by material improvement. The biggest difficulty of the multi-layer structure type wave absorbing material is the impedance matching problem. Generally, electromagnetic waves have different entering capacities along with the change of the magneto-electric characteristics of the material in the process of entering the wave-absorbing material. The invention is directed to magnetic materials, and the entering capability of electromagnetic waves tends to be weakened gradually along with the gradient change (such as from low to high) of the magnetic permeability of the materials. Therefore, the wave absorber with the multilayer structure and the impedance gradual change structure is adopted, and electromagnetic waves entering the space can enter the absorption layer as much as possible to be lost and absorbed through the matching effect of the impedance matching layer. In the invention, spherical carbonyl iron powder with low dielectric constant, low magnetic conductivity and good high-frequency performance is used as the outermost layer; taking flaky FeSiAl with strong medium-frequency absorption as a transition layer; the high-frequency rare earth soft magnetic material with high dielectric constant, high magnetic conductivity and large low-frequency loss is used as a high-loss bottom layer. Finally, the radar stealth wave-absorbing material with broadband absorption capacity is obtained through a comprehensive optimization process.
The beneficial effects obtained by the technical scheme are as follows:
(1) The wave-absorbing material with the composite structure adopts a gradient structure design, so that the magneto-electric property of the material can be exerted to the greatest extent, specifically, carbonyl iron powder with low dielectric constant and low magnetic conductivity is used as the outermost layer, and the wave-absorbing material generates wave-absorbing efficiency in a high-frequency range; the flaky FeSiAl with strong medium frequency absorption is used as a transition layer, and the flaky FeSiAl with strong medium frequency absorption is used for generating wave absorption efficiency in a medium frequency range; the high-frequency rare earth soft magnetic material with high dielectric constant, high magnetic conductivity and large low-frequency loss is used as a high-loss bottom layer, and the high-frequency rare earth soft magnetic material generates wave absorbing effect in a low frequency band.
(2) The wave-absorbing material with the gradient composite structure can bear higher mechanical property and thermal shock resistance, which lays a foundation for subsequent stealth bearing and multifunctional integration.
Drawings
Fig. 1 is a schematic structural diagram of a wave-absorbing material with a gradient composite structure according to an embodiment.
Fig. 2 is a graph showing the reflectivity of radar waves of the wave-absorbing material having the gradient composite structure provided in example 1.
Fig. 3 is a graph showing the reflectivity of radar waves of the wave-absorbing material having the gradient composite structure provided in example 2.
Fig. 4 is a graph showing the reflectivity of radar waves of the wave-absorbing material of the composite structure having a gradient provided in comparative example 1.
Detailed Description
The invention is further illustrated below with reference to specific examples. The scope of the invention is not limited in this respect.
Example 1
A wave-absorbing material with a composite structure gradient is shown in figure 1, and comprises a high-frequency rare earth soft magnet, iron-silicon-aluminum and an iron carbonyl outer layer from inside to outside in sequence; the specific implementation is as follows:
(1) 20wt% of epoxy resin 3D printing liquid, 70wt% of high-frequency rare earth soft magnetic, 5wt% of nano silicon dioxide dispersing agent and 5wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, a 3D printing high-frequency rare earth soft magnetic wave-absorbing coating with the thickness of 0.8mm is adopted on a metal substrate.
(2) Mixing 50wt% of epoxy resin 3D printing solution, 20wt% of Fe-Si-Al, 20wt% of nano silicon dioxide dispersing agent and 10wt% of cyclohexanone preliminarily, and slowly stirring for 2 hours by a stirrer, wherein the thickness of the Fe-Si-Al wave-absorbing coating is 0.3mm by adopting 3D printing on the surface of the high-frequency rare earth soft magnetic wave-absorbing coating obtained in the step (1); forming the Fe-Si-Al/high frequency rare earth soft magnetic wave-absorbing coating.
(3) 50wt% of epoxy resin 3D printing solution, 10wt% of carbonyl iron, 30wt% of nano silicon dioxide dispersing agent and 10% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, 3D printing carbonyl iron wave absorbing paint with the thickness of 0.2mm is adopted on the iron silicon aluminum/high frequency rare earth soft magnetic wave absorbing coating obtained in the step (2); forming an Fe-Si-Al/high-frequency rare earth soft magnetic/carbonyl iron wave-absorbing coating, curing for 1h at 200 ℃ to obtain a wave-absorbing material with a composite structure gradient, and testing by a large plate bow method (national standard test method GJB 2038A-2011-RL) to obtain the wave-absorbing performance. As shown in FIG. 2, the material prepared in example 1 has a maximum reflectivity of-42 dB in the 2-18GHz band, and an effective band coverage width of 6.5GHz. Table 1 shows the mechanical properties of the examples.
Example 2
(1) 20wt% of epoxy resin 3D printing liquid, 70wt% of high-frequency rare earth soft magnetic, 5wt% of nano silicon dioxide dispersing agent and 5wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, the 3D printing high-frequency rare earth soft magnetic wave-absorbing coating with the thickness of 1mm is adopted on a metal substrate.
(2) 50wt% of epoxy resin 3D printing liquid, 20wt% of iron silicon aluminum, 20wt% of nano silicon dioxide dispersing agent and 10wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, 3D printing of the iron silicon aluminum wave-absorbing coating is adopted on the basis of (1), wherein the thickness is 0.4mm; forming the Fe-Si-Al/high frequency rare earth soft magnetic wave-absorbing coating,
(3) 50wt% of epoxy resin 3D printing liquid, 10wt% of carbonyl iron, 30wt% of nano silicon dioxide dispersing agent and 10wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, 3D printing carbonyl iron wave-absorbing paint with the thickness of 0.4mm is adopted on the basis of the step (2); forming Fe-Si-Al/high-frequency rare earth soft magnetic/carbonyl iron wave-absorbing coating; solidifying for 1h at 200 ℃ to obtain the wave-absorbing material with the composite structure gradient. The performance of the material prepared in example 2 is shown in FIG. 3, the maximum reflectivity of the material in the frequency band of 2-18GHz is-45 dB, and the coverage width of the effective frequency band is 5GHz. Table 1 shows the mechanical properties of the examples.
Comparative example 1
(1) 50wt% of epoxy resin 3D printing solution, 10wt% of carbonyl iron, 30wt% of nano silicon dioxide dispersing agent and 10wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed by a stirrer, 3D printing carbonyl iron paint is adopted on a metal substrate, wherein the thickness is 0.2mm.
(2) 50wt% of epoxy resin 3D printing liquid, 20wt% of iron silicon aluminum, 20wt% of nano silicon dioxide dispersing agent and 10wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, 3D printing of the iron silicon aluminum wave-absorbing coating is adopted on the basis of the step (1), wherein the thickness is 0.3mm; forming the Fe-Si-Al/carbonyl iron wave-absorbing coating,
(3) 20wt% of epoxy resin 3D printing liquid, 70wt% of high-frequency rare earth soft magnetic, 5wt% of nano silicon dioxide dispersing agent and 5wt% of cyclohexanone are initially mixed, and after the mixture is stirred for 2 hours at a low speed, 3D printing high-frequency rare earth soft magnetic wave-absorbing paint with the thickness of 0.8mm is adopted on the basis of (2); forming high-frequency rare earth soft magnetic/Fe-Si-Al/carbonyl iron wave-absorbing coating; solidifying for 1h at 200 ℃ to obtain the wave-absorbing material with the composite structure gradient. The performance is shown in figure 4, the maximum reflectivity in the frequency band of 2-18GHz is-20 dB, and the coverage width of the effective frequency band is 2.5GHz. Table 1 shows the mechanical properties of the examples.
Table 1 mechanical properties comparison table
Claims (7)
1. A wave absorbing material having a composite structure, comprising: the high-frequency rare earth soft magnetic layer is adsorbed on the substrate, the FeSiAl layer is formed on the high-frequency rare earth soft magnetic layer, and the carbonyl iron layer is formed on the FeSiAl layer, wherein the mass ratio of the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carbonyl iron layer to the wave absorbing material is in gradient change; the mass ratio of the high-frequency rare earth soft magnetic layer to the FeSiAl layer to the carbonyl iron layer in the wave-absorbing material is 60-80:20-15:10-5 respectively; the thickness of the high-frequency rare earth soft magnetic layer, the FeSiAl layer and the carbonyl iron layer is 0.8-1.0:0.3-0.4:0.2-0.4mm respectively.
2. The wave-absorbing material with a composite structure according to claim 1, wherein the thickness of the wave-absorbing material with a composite structure is 0.8-3.0 mm.
3. The wave-absorbing material with composite structure according to claim 1, wherein the high-frequency rare earth soft magnetic has a chemical formula of a a Co b Fe c Wherein A is one of Y, pr, nd, er, gd, tb, dy, ho rare earth elementsSeed, and A a Co b Wherein the content of A atoms is 30-35%, the content of Co atoms is 25-35%, and the content of Fe atoms is 30-45%.
4. The wave-absorbing material with composite structure according to claim 1, wherein the broadband wave-absorbing performance of the wave-absorbing material with composite structure is that the maximum reflectivity is-30 to-45 dB, and the effective frequency band coverage width is 4-6.5GHz.
5. The method for producing a wave-absorbing material having a composite structure according to any one of claims 1 to 4, comprising:
(1) Mixing high-frequency rare earth soft magnet, a solvent and a 3D printing liquid to obtain a mixed solution A, mixing FeSiAl, the solvent and the 3D printing liquid to obtain a mixed solution B, and mixing carbonyl iron powder, the solvent and the 3D printing liquid to obtain a mixed solution C;
(2) Printing the mixed solution A on the surface of a substrate to form a high-frequency rare earth soft magnetic layer by a 3D printing technology, printing the mixed solution B on the surface of the high-frequency rare earth soft magnetic layer to obtain a high-frequency rare earth soft magnetic layer/FeSiAl layer, printing the mixed solution C on the surface of the FeSiAl layer to obtain the high-frequency rare earth soft magnetic layer/FeSiAl layer/carbonyl iron layer, and curing to obtain the wave-absorbing material with the composite structure.
6. The method for preparing a wave-absorbing material with a composite structure according to claim 5, wherein the solvent is one or more of acetone, n-hexane, cyclohexanone, butylbenzene, xylene and isobutanol.
7. The method for preparing a wave-absorbing material having a composite structure according to claim 5, wherein the curing process is curing at 100-300 ℃ for 1-2 hours.
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US5872534A (en) * | 1997-10-01 | 1999-02-16 | Fair-Rite Products Corporation | High frequency broadband absorption structures |
CN102501492A (en) * | 2011-09-29 | 2012-06-20 | 湖南金戈新材料有限责任公司 | Preparation technology of centimetre wave-millimeter wave compatible absorbing material |
CN113072382A (en) * | 2021-04-22 | 2021-07-06 | 太仓派欧技术咨询服务有限公司 | Broadband wave-absorbing material based on 3D printing and preparation method thereof |
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US5872534A (en) * | 1997-10-01 | 1999-02-16 | Fair-Rite Products Corporation | High frequency broadband absorption structures |
CN102501492A (en) * | 2011-09-29 | 2012-06-20 | 湖南金戈新材料有限责任公司 | Preparation technology of centimetre wave-millimeter wave compatible absorbing material |
CN113072382A (en) * | 2021-04-22 | 2021-07-06 | 太仓派欧技术咨询服务有限公司 | Broadband wave-absorbing material based on 3D printing and preparation method thereof |
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Title |
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许志远 等.不同电磁特性吸收剂的多层宽带吸波材料设计.材料科学与工程学报.2021,第39卷(第2期),第199-204页. * |
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