CN109720027B - High-temperature-resistant structural wave-absorbing material based on metal coating and preparation method thereof - Google Patents

High-temperature-resistant structural wave-absorbing material based on metal coating and preparation method thereof Download PDF

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CN109720027B
CN109720027B CN201910164292.5A CN201910164292A CN109720027B CN 109720027 B CN109720027 B CN 109720027B CN 201910164292 A CN201910164292 A CN 201910164292A CN 109720027 B CN109720027 B CN 109720027B
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temperature
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resistant
absorbing
fiber cloth
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CN109720027A (en
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杜作娟
汪翔宇
姜超
黄小忠
赵子翔
张乾诚
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Central South University
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Abstract

The invention discloses a high-temperature-resistant structure wave-absorbing material based on a metal coating and a preparation method thereof. The high-temperature-resistant structure wave-absorbing material is composed of a wave-absorbing body of a high-temperature-resistant fiber cloth coating structure; the structural wave absorber is formed by a group of structural wave absorber units or formed by superposing more than two groups of structural wave absorber units; the structural wave absorber unit comprises a medium substrate layer and a resistance layer on the surface of the medium substrate layer. The preparation method comprises the steps of sputtering a high-temperature-resistant metal material to the surface of the high-temperature-resistant fiber cloth by adopting a magnetron sputtering process to obtain a resistance layer; covering the impedance layer on the surface of the dielectric substrate layer to obtain a group of structural wave absorber units; the high-temperature-resistant structural wave-absorbing material which can resist the high temperature of at least over 700 ℃, has better high temperature resistance and oxidation resistance and has wider wave-absorbing bandwidth is obtained by adopting a group of structural wave-absorbing body units of high-temperature-resistant fiber cloth or a plurality of groups of laminated structural wave-absorbing body units and sewing.

Description

High-temperature-resistant structural wave-absorbing material based on metal coating and preparation method thereof
Technical Field
The invention relates to a wave-absorbing material, in particular to a wave-absorbing material which is high-temperature resistant, oxidation resistant and wide in wave-absorbing bandwidth, and a preparation method thereof, belonging to the technical field of wave-absorbing materials.
Background
With the development of modern military technology, stealth technology is applied to various complex environments. For example, the working temperature of components such as a tail nozzle, a nose cone cap, a wing front edge and the like of air weaponry such as fighters, cruise missiles and the like can reach 700 ℃ or even more than 1000 ℃, the reflection of radar waves is strong, and the components become important factors influencing the stealth performance of novel weaponry. Most magnetic materials lose the wave absorbing effect at the working temperature of high-temperature parts because the Curie temperature of the magnetic materials is lower than 700 ℃. Therefore, most of the high-temperature wave-absorbing materials are electric loss wave-absorbing materials, and compared with the magnetic wave-absorbing materials applied at normal temperature, the high-temperature wave-absorbing materials have narrower absorption frequency band and poorer low-frequency wave-absorbing effect. How to improve the wave absorbing performance of the high-temperature wave absorbing material is one of the contents which are always explored in the research of the high-temperature stealth material.
The material research related to high-temperature stealth at home and abroad mainly comprises carbon materials, silicon carbide, metal oxides and the like, and the modification mode mainly comprises the steps of improving the high-temperature resistance of the material through coating modification and improving the loss through doping modification. Patents CN105861977A, CN108821778A, and CN103880426A disclose high temperature resistant wave-absorbing materials, respectively, and several disclosed wave-absorbing materials have better high temperature resistance, but the wave-absorbing frequency band lower than-10 dB is narrower. The high-temperature resistant wave-absorbing material usually takes a ceramic material or a metal oxide as a matrix, has high dielectric constant, inevitably causes narrow effective bandwidth, is difficult to meet application requirements, and can expand wave-absorbing bandwidth through structural stealth design.
The structural stealth is to realize matching and absorption of incident electromagnetic waves by utilizing an artificially constructed actual structure or circuit, and the structural stealth takes a dielectric material insensitive to electromagnetic parameters in broadband as a matrix, and arranges a periodic circuit structure consisting of a resistance film, a circuit element or a frequency selection surface on the surface of the matrix to form a single-layer or multi-layer laminated wave-absorbing structure. Several multi-layer structure wave-absorbing materials are respectively disclosed in patents US2599944A, CN108749229A and CN108819384A, and have good wave-absorbing performance and a wider absorption band at normal temperature.
Patents CN107039778A, CN107141021A, CN106042515A, and CN106007804A disclose several high temperature resistant structural wave-absorbing materials, respectively, and adopt materials such as metal oxide ceramics and conductive glass to prepare a wave-absorbing structure based on a frequency selective surface, which has better high temperature resistance and broadband wave-absorbing performance, but the wave-absorbing performance changes greatly with the temperature rise.
Disclosure of Invention
Aiming at the defects of the high-temperature resistant wave-absorbing material in the background technology, the invention aims to provide the high-temperature resistant structure wave-absorbing material which can resist the high temperature of at least 700 ℃, has better high-temperature resistance and oxidation resistance and has wider wave-absorbing bandwidth.
The invention also aims to provide a simple and low-cost method for preparing the high-temperature-resistant structural wave-absorbing material.
In order to realize the technical purpose, the invention provides a high-temperature-resistant structure wave-absorbing material based on a metal coating, which is composed of a wave-absorbing body of a high-temperature-resistant fiber cloth coating structure; the structural wave absorber is formed by a group of structural wave absorber units or formed by superposing more than two groups of structural wave absorber units; the structure wave absorber unit comprises a medium substrate layer and a resistance layer on the surface of the medium substrate layer, wherein the medium substrate layer is an oxide fiber reinforced oxide aerogel composite material, and the resistance layer is high-temperature resistant fiber cloth containing a high-temperature resistant metal material coating.
In a preferable scheme, the thickness of the dielectric substrate layer is 5-10 mm.
In a preferable scheme, the thickness of the high-temperature-resistant metal material coating is 10-100 nm.
In the preferred scheme, the structural wave absorber is formed by overlapping 1-3 groups of structural wave absorber units.
Preferably, the oxide fiber reinforced oxide aerogel composite comprises a silica aerogel composite reinforced with a silica fiber felt or a silica aerogel composite reinforced with continuous mullite fiber. The selected oxide fiber reinforced oxide aerogel composite material can not only ensure the wave-absorbing performance and high temperature resistance of the wave-absorbing material product, but also ensure that the wave-absorbing material has lower surface density and thermal conductivity.
In a preferred embodiment, the high-temperature-resistant metal material coating on the surface of the high-temperature-resistant fiber cloth containing the high-temperature-resistant metal material coating is a uniform continuous film or a frequency selective surface.
Preferably, the frequency selective surface is a periodic array of square patches or a periodic array of a square-hole grid, as shown in fig. 3 and 4.
In a more preferable scheme, the temperature coefficient range of the high-temperature resistant metal material coating is 0-50 ppm/DEG C.
In a preferred embodiment, the high temperature resistant metal material includes nichrome, nichrome alloy, chromealnd alloy, ferrochromium alloy, or ferrochromium aluminum manganese alloy. The selected high-temperature resistant metal materials have high working temperature, low temperature coefficient of resistivity and small electrical property change with temperature, and can still maintain the original wave-absorbing performance at high temperature.
Preferably, the high-temperature resistant fiber cloth comprises quartz fiber cloth, silicon carbide fiber cloth or boron nitride fiber cloth.
The invention also provides a preparation method of the high-temperature-resistant structure wave-absorbing material based on the metal coating, which comprises the following steps:
1) preparing a medium substrate layer;
2) sputtering a high-temperature-resistant metal material to the surface of the high-temperature-resistant fiber cloth by adopting a magnetron sputtering process to obtain a resistance layer;
3) covering the impedance layer on the surface of the dielectric substrate layer to obtain a group of structural wave absorber units;
4) stacking more than two groups of structure wave absorber units from bottom to top to obtain a plurality of groups of structure wave absorber units;
5) and (3) adopting a group of structural wave absorbing body units or a plurality of groups of structural wave absorbing body units of high-temperature resistant fiber cloth and sewing to obtain the wave absorbing fabric.
In a preferred scheme, the magnetron sputtering process conditions are as follows: the magnetron sputtering source is a direct current source, the sputtering voltage is 1-10V, the sputtering time is 0.5-10 min, the sputtering atmosphere is nitrogen or argon, the background vacuum degree is not more than 5 multiplied by 10-4Pa。
Compared with the prior art, the technical scheme of the invention has the advantages that:
(1) the high-temperature-resistant structure wave-absorbing material adopts high-temperature-resistant and oxidation-resistant ceramic or alloy materials, and can resist high temperature of at least 700 ℃, so that the whole wave-absorbing material has better high-temperature resistance and excellent oxidation resistance.
(2) The high-temperature-resistant structure wave-absorbing material adopts the low-density aerogel material, has smaller overall surface density, reduces the weight of the product, meets the light-weight requirement of components, has lower dielectric constant, and is easier to realize broadband wave absorption compared with bulk ceramic materials.
(3) The wave-absorbing material layer of the high-temperature resistant structure has lower thermal conductivity, so that the wave-absorbing material layer has better heat-insulating property, and can realize integration of multiple functions of stealth, heat insulation, heat prevention and the like.
(4) The high-temperature-resistant structure wave-absorbing material provided by the invention adopts a metal material with a low resistance temperature coefficient to prepare the impedance layer, and the performance of the impedance layer is less influenced by temperature, so that the wave-absorbing performance is not easy to change along with the temperature rise.
(5) The high-temperature-resistant structure wave-absorbing material disclosed by the invention adopts magnetron sputtering to prepare the metal film, the thickness of the film can be controlled through sputtering conditions, and the precise impedance matching design is realized.
Drawings
FIG. 1 is a structural absorber consisting of two sets of structural absorber units;
FIG. 2 is a radar reflectivity curve of the microwave absorbing material of the high temperature resistant structure of example 1;
FIG. 3 is a periodic array of square hole grids;
fig. 4 is a periodic array of square patches.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The invention relates to a high-temperature-resistant structure wave-absorbing material based on a metal coating, which is shown in figure 1 and comprises two groups of structure wave-absorbing bodies, wherein each structure wave-absorbing body comprises a medium substrate layer and a resistance layer from bottom to top, the medium substrate layer is made of a quartz fiber reinforced silica aerogel composite material, and the resistance layer is made of nickel-chromium alloy coated quartz fiber cloth. The preparation method comprises the following steps:
(1) preparing a medium substrate: selecting a quartz fiber reinforced silica aerogel composite material according to design requirements, preparing the quartz fiber reinforced silica aerogel composite material by adopting a sol-gel process, and finally processing the composite material to 7.5mm by adopting a mechanical processing method to prepare a medium substrate layer 1 and a medium substrate layer 2 with the thickness of 7.5 mm;
(2) preparing a resistance layer: adopting magnetron sputtering technology, sputtering the nickel-chromium alloy for preparing the impedance layer on the surface of the quartz fiber cloth to form a uniform continuous film, respectively preparing the impedance layer 1 and the impedance layer 2, wherein a magnetron sputtering source is a direct current source, the sputtering voltage is 1V, the sputtering atmosphere is nitrogen, the background vacuum degree is 5 multiplied by 10-4Pa, sputtering for 0.5min to obtain a resistance layer 1, and sputtering for 1min to obtain a resistance layer 2.
(3) Covering the impedance layer 1 prepared in the step (2) on the surface of the medium substrate layer 1 to obtain a structure wave absorber 1; covering the impedance layer 2 prepared in the step (2) on the surface of the medium substrate layer 2 to obtain a structure wave absorber 2;
(4) laminating the structure wave absorber 1 and the structure wave absorber 2 prepared in the step (3) from bottom to top to obtain a double-layer wave absorbing structure;
(5) and (5) coating the multilayer wave-absorbing structure obtained in the step (4) by using quartz fiber cloth and sewing to complete the preparation of the high-temperature-resistant structure wave-absorbing material.
The radar reflectivity curve of the high-temperature-resistant structure wave-absorbing material is shown in figure 2, and the reflectivity of the radar wave-absorbing material is less than-10 dB in the range of 4.5-15 GHz at room temperature.
Example 2
The invention relates to a high-temperature-resistant structure wave-absorbing material based on a metal coating, which consists of a group of structure wave-absorbing bodies, wherein each structure wave-absorbing body comprises a medium base layer and a resistance layer from bottom to top, the medium base layer is a continuous mullite fiber reinforced silica aerogel composite material, and the resistance layer is nickel-chromium-iron alloy coated boron nitride fiber cloth. The preparation method comprises the following steps:
(1) preparing a medium substrate: selecting a quartz fiber reinforced silica aerogel composite material according to design requirements, preparing the continuous mullite fiber reinforced silica aerogel composite material by adopting a sol-gel process, and finally processing the composite material to 7.5mm by adopting a mechanical processing method to prepare a medium substrate layer with the thickness of 7.5 mm;
(2) preparing a resistance layer: adopting magnetron sputtering technology to sputter the nickel-chromium-iron alloy for preparing the impedance layer on the surface of the boron nitride fiber cloth to form a uniform continuous film, wherein a magnetron sputtering source is a direct current source, the sputtering voltage is 3V, the sputtering atmosphere is argon, the background vacuum degree is 1 multiplied by 10-4Pa, and the sputtering time is 1 min.
(3) Covering the impedance layer prepared in the step (2) on the surface of the medium substrate layer to obtain a group of structure wave absorbers;
(4) and (4) coating and packaging the group of structural wave absorbing bodies in the step (3) by using quartz fiber cloth to finish the preparation of the high-temperature-resistant structural wave absorbing material.
The radar reflectivity of the wave-absorbing material with the high-temperature resistant structure is tested, the reflectivity is less than-10 dB in the range of 8-12 GHz at room temperature, and an absorption peak less than-30 dB is obtained at the 10GHz frequency point.
Example 3
The invention relates to a high-temperature-resistant structure wave-absorbing material based on a metal coating, which is shown in figure 1 and comprises two groups of structure wave-absorbing bodies, wherein each structure wave-absorbing body comprises a medium substrate layer and a resistance layer from bottom to top, the medium substrate layer is made of a quartz fiber reinforced silica aerogel composite material, and the resistance layer is made of nickel-chromium-neodymium alloy coated silicon carbide fiber cloth. The preparation method comprises the following steps:
(1) preparing a medium substrate: selecting a quartz fiber reinforced silica aerogel composite material according to design requirements, preparing the quartz fiber reinforced silica aerogel composite material by adopting a sol-gel process, and finally processing the composite material to 5mm by adopting a mechanical processing method to prepare a medium substrate layer 1 and a medium substrate layer 2 with the thickness of 5 mm;
(2) preparing a resistance layer: firstly, cutting quartz fiber cloth into a grid array shown in fig. 3, wherein the size of a square hole is 1mm multiplied by 1mm, and the line width of a grid is 1 mm; then adopting magnetron sputtering process to prepareSputtering Ni-Cr-Nd alloy of the resistance layer on the surface of silicon carbide fiber cloth to form a frequency selective surface (as shown in figure 3), respectively preparing a resistance layer 1 and a resistance layer 2, wherein a magnetron sputtering source is a direct current source, the sputtering voltage is 3V, the sputtering atmosphere is argon, and the background vacuum degree is 1 multiplied by 10-4And Pa, sputtering for 1min to obtain a resistance layer 1, and sputtering for 2.5min to obtain a resistance layer 2.
(3) Covering the impedance layer 1 prepared in the step (2) on the surface of the medium substrate layer 1 to obtain a structure wave absorber 1; covering the impedance layer 2 prepared in the step (2) on the surface of the medium substrate layer 2 to obtain a structure wave absorber 2;
(4) laminating the structure wave absorber 1 and the structure wave absorber 2 prepared in the step (3) from bottom to top to obtain a double-layer wave absorbing structure;
(5) and (5) coating the multilayer wave-absorbing structure obtained in the step (4) by using quartz fiber cloth and sewing to complete the preparation of the high-temperature-resistant structure wave-absorbing material.
The radar reflectivity of the wave-absorbing material with the high-temperature resistant structure is tested, and is smaller than-10 dB within the range of 6-18 GHz at room temperature.

Claims (7)

1. A high temperature resistant structure wave-absorbing material based on metal coating is characterized in that:
the wave absorber is composed of a high-temperature resistant fiber cloth coating structure;
the structural wave absorber is formed by a group of structural wave absorber units or formed by superposing more than two groups of structural wave absorber units;
the structural wave absorber unit comprises a medium substrate layer and a resistance layer on the surface of the medium substrate layer, wherein the medium substrate layer is an oxide fiber reinforced oxide aerogel composite material, and the resistance layer is high-temperature resistant fiber cloth containing a high-temperature resistant metal material coating;
the oxide fiber reinforced oxide aerogel composite material comprises a quartz fiber felt reinforced silica aerogel composite material or a continuous mullite fiber reinforced silica aerogel composite material;
the temperature coefficient range of the high-temperature resistant metal material coating is 0 ~ 50 ppm/DEG C;
the high-temperature resistant fiber cloth comprises quartz fiber cloth, silicon carbide fiber cloth or boron nitride fiber cloth.
2. The metal coating-based high-temperature-resistant structural wave-absorbing material as claimed in claim 1, wherein the thickness of the dielectric substrate layer is 5 ~ 10mm, and the thickness of the high-temperature-resistant metal material coating layer is 10 ~ 100 nm.
3. The high-temperature-resistant structural wave-absorbing material based on the metal coating as claimed in claim 1, wherein: the high-temperature resistant metal material coating on the surface of the high-temperature resistant fiber cloth containing the high-temperature resistant metal material coating is a uniform continuous film or a frequency selective surface.
4. The high-temperature-resistant structural wave-absorbing material based on the metal coating as claimed in claim 3, wherein: the frequency selective surface is a periodic array formed by square patches or a periodic array formed by a square hole grid.
5. The high temperature resistant structural wave absorbing material in accordance with any one of claims 1 and 3 ~ 4, wherein the high temperature resistant metallic material comprises nichrome, chromealnd, ferrochromium, or ferrochromium-alumel.
6. The preparation method of the high-temperature resistant structure wave-absorbing material based on the metal coating of claim 1 ~ 5 is characterized by comprising the following steps:
1) preparing a medium substrate layer;
2) sputtering a high-temperature-resistant metal material to the surface of the high-temperature-resistant fiber cloth by adopting a magnetron sputtering process to obtain a resistance layer;
3) covering the impedance layer on the surface of the dielectric substrate layer to obtain a group of structural wave absorber units;
4) stacking more than two groups of structure wave absorber units from bottom to top to obtain a plurality of groups of structure wave absorber units;
5) and (3) adopting a group of structural wave absorbing body units or a plurality of groups of structural wave absorbing body units of high-temperature resistant fiber cloth and sewing to obtain the wave absorbing fabric.
7. The method for preparing the high temperature resistant structural wave-absorbing material based on the metal coating according to claim 6, characterized in that the magnetron sputtering process conditions are that a magnetron sputtering source is a direct current source, the sputtering voltage is 1 ~ 10V, the sputtering time is 0.5 ~ 10min, the sputtering atmosphere is nitrogen or argon, the background vacuum degree is not more than 5 x 10-4Pa。
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CN112428637B (en) * 2020-11-06 2022-08-05 航天特种材料及工艺技术研究所 Ablation-resistant high-temperature wave-absorbing material and preparation method thereof
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CN106003864B (en) * 2016-05-18 2017-11-24 中国人民解放军国防科学技术大学 High temperature resistant radar & infrared stealth materials based on frequency-selective surfaces and preparation method thereof
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