Preparation method of laser-infrared-radar compatible multispectral inhibition ceramic material

Abstract

The invention relates to a preparation method of a laser-infrared-radar compatible multispectral inhibition ceramic material, which comprises the following steps: by taking iron oxide, manganese oxide, magnesium oxide, copper oxide, nickel oxide and cobalt sesquioxide as raw materials, carrying out ball milling, mixing and drying, granulating, pressing into a green body sheet, and calcining to obtain a high-entropy ceramic substrate; depositing a low-refractive-index material L, a defect layer material S and a high-refractive-index material H on the high-entropy ceramic substrate according to a film layer structure as a substrate (LH) (LH) S (LH) Air or a substrate (LH) S (LH) (LH) (LH) Air by adopting a sputtering process; the prepared material has the multispectral protection characteristic compatible with laser / infrared / radar, and in the aspect of laser protection, the reflectivity can reach 2.19%, 1.78% and 2.9% at the characteristic laser points of 1.06 m, 1.54 m and 10.6 m; in the aspect of infrared protection, the reflectivity at the infrared absorption frequency bands of 3-5 m and 8-14 m can reach 97%; in the aspect of radar protection, under the ultra-thin 2.2 mm thickness, the effective absorption bandwidth of 3.2 GHz and the minimum reflection loss of-67.4 dB are achieved. The materials selected by the system are all high-temperature-resistant materials and can adapt to a high-temperature service environment.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a laser-infrared-radar compatible multispectral suppression ceramic material, and belongs to the technical field of functional ceramic materials. BACKGROUND

[0002] With the rapid development and diversification of modern detection technology, traditional single frequency band protection materials have been difficult to cope with the threat of multi-spectral detection in complex environments. Especially in the field of aerospace and high-end equipment protection, detection systems are moving towards multi-band, high precision and intelligentization, covering multiple frequency bands such as laser, infrared and radar. Therefore, developing new materials that can realize compatible suppression function in a wide spectral range has become an important research direction in current material science. Under this background, multispectral compatible suppression materials not only need to have excellent optical and electromagnetic properties, but also must adapt to extreme service environments such as high temperature and high load, which puts high requirements on the comprehensive performance of the materials.

[0003] As a typical representative, the surface thermal protection and structure of aerospace vehicles need to withstand high temperature oxidation and thermal shock of thousands of degrees Celsius for a long time during reentry into the atmosphere or high-speed flight. Traditional resin-based or metal-based protection materials are prone to oxidation, decomposition or structural failure under these conditions, losing their protective function. Therefore, ceramic matrix composites with excellent thermal stability and oxidation resistance, especially high-entropy ceramic systems that have emerged in recent years, are considered as ideal high-temperature multi-spectral functional carrier materials due to their adjustable composition, entropy stabilization effect and excellent high-temperature mechanical properties.

[0004] In the prior art, the main technical path to achieve multispectral compatibility can be divided into two categories: multi-element configuration design and multi-layer film system stacking. The former is represented by metamaterials, which design and integrate artificial atoms or microstructures with different resonance characteristics on a sub-wavelength scale to achieve response regulation for specific wavebands. Although this type of structure is flexible in design, it often relies on expensive and complex micro-nano manufacturing processes such as electron beam lithography and nano-imprinting, making it difficult to achieve large-scale preparation. Moreover, the coupling effect between structure units will drift with increasing temperature, affecting the performance stability at high temperatures. The latter is mainly based on photonic crystals, which form photonic band gaps and photonic localizations through the periodic arrangement of dielectric constants on a wavelength scale, thereby selectively suppressing or transmitting specific wavebands. Photonic crystals have shown good results in laser and infrared compatibility, but due to their highly sensitive band structure to wavelength, it is difficult to expand to centimeter / millimeter wave radar bands while maintaining infrared laser suppression. In addition, existing photonic crystal and metamaterial systems often use indium tin oxide (ITO) or polymer resin as the functional phase or bonding medium, which generally has a temperature resistance lower than 300°C, unable to meet the long-term service requirements in higher temperature environments. Based on the above bottlenecks, developing a new type of compatible protective material that can cover laser, infrared, and radar wavebands and has high temperature adaptability has important strategic significance and engineering application value. SUMMARY

[0005] The purpose of the present application is to address the needs of multispectral detection threats and high temperature service environments by providing a preparation method for a laser-infrared-radar compatible multispectral suppression ceramic material. The present application uses high-entropy ceramics as the substrate, low-refractive materials / defect layer materials / high-refractive materials as the functional coating, designs a multi-layer micro-nano structure using FDTD simulation and Needle algorithm, and uses magnetron sputtering technology for actual preparation. Finally, the obtained material has excellent laser suppression, infrared protection, and electromagnetic wave absorption properties, and can withstand temperatures above 800°C.

[0006] The technical solution of the present application is: based on electromagnetic simulation design (FDTD), film system optimization algorithm (Needle algorithm), and magnetron sputtering process, a photonic crystal composite structure is designed, which uses high-entropy ceramics as the substrate and low-refractive materials / defect layer materials / high-refractive materials as the multi-layer functional film system. This structure achieves high-efficiency infrared protection in the infrared waveband through periodic design, effectively absorbs laser in the laser waveband by introducing a defect layer, and realizes wideband electromagnetic wave absorption in the radar waveband through magnetoelectric coupling mechanism. In terms of preparation process, magnetron sputtering technology is used to achieve nanoscale precision film layer control, ensuring film-substrate bonding strength and high temperature stability, while effectively avoiding interfacial diffusion and element segregation at high temperatures.

[0007] The specific technical scheme of the present application is: a preparation method of a laser-infrared-radar compatible multi-spectrum suppression ceramic material, which comprises the following specific steps: A. Preparation of high-entropy ceramic material: taking iron oxide, manganese oxide, magnesium oxide, copper oxide, nickel oxide and cobalt sesquioxide as raw materials, uniformly ball-milling, drying, granulating, and pressing into a green sheet, and then putting into a furnace for calcination to obtain a high-entropy ceramic base; B. Deposition of thin film: using a sputtering process to deposit low-refractive-index material L, defect layer material S and high-refractive-index material H on the high-entropy ceramic base obtained in step A, and by adjusting film layer thickness, vacuum degree, gas flow and sputtering power and other parameters, a ceramic material with laser-infrared-radar compatible multi-spectrum suppression performance is prepared; wherein the prepared film layer structure is: base|(LH)(LH)(LH)S(LH)|Air or base|(LH)S(LH)(LH)(LH)|Air.

[0008] Preferably, the iron oxide is ferrous oxide, cobalt sesquioxide or magnetite.

[0009] Preferably, the molar ratio of iron oxide, manganese oxide, magnesium oxide, copper oxide, nickel oxide and cobalt sesquioxide is 1:(0.5-4):(0.5-4):(0.5-4):(0.5-4):(0.5-4).

[0010] Preferably, the calcination temperature is 800-1500℃, and the holding time is 2-12h.

[0011] Preferably, the low-refractive-index material L is MgF2, MgO, TiO2 or HfO2; the defect layer material S is Si; the high-refractive-index material H is Ge or Te; based on FDTD software, the film layer is designed, and based on the design results, the Needle algorithm is used to further optimize the film layer thickness, thereby further improving the compatibility of infrared and laser. The structure after optimization is: base|(LH)(LH)(LH)S(LH)|Air or base|(LH)S(LH)(LH)(LH)|Air, L represents a low-refractive-index film layer, H represents a high-refractive-index film layer, and S represents a Si defect layer, and the base is a high-entropy ceramic.

[0012] According to the quarter wavelength principle, the film layer thickness matching relationship is: preferably, the film layer thickness is: the thickness of the low-refractive-index material film layer is 100-3000nm; the thickness of the high-refractive-index material film layer is 300-1500nm; and the thickness of the defect layer material is 20-500nm.

[0013] Based on the above film system, a low refractive index material / defect layer material / high refractive material is used as the target material for plating on the high-entropy ceramic substrate, and the plating parameters are: the vacuum degree is preferably 0.01-10 Pa; the gas flow is 5-100 ml / min; the sputtering power is 30-300 W; and finally a laser-infrared-radar compatible multi-spectral suppression ceramic material is obtained.

[0014] Beneficial effects: Compared with the prior art, the technology adopts the construction method of wave-absorbing substrate + photonic crystal film, and realizes the effect of laser-infrared-radar compatible multi-spectral compatible suppression. In terms of laser protection, the reflectivity at the characteristic laser points of 1.06, 1.54 and 10.6 µm can reach 2.19%, 1.78% and 2.9%. In terms of infrared protection, the reflectivity in the infrared absorption frequency band of 3-5 µm and 8-14 µm can reach 97%. In terms of radar protection, under the thickness of 2.2 mm, the effective absorption bandwidth is 3.2 GHz and the minimum reflection loss is -67.4 dB, and the multi-protection effect of laser-infrared-radar is achieved. In addition, the materials selected in this system are all high-temperature resistant and can adapt to complex service environments. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 is a laser suppression performance graph of Example 1; Figure 2 is an infrared absorption performance graph of Example 1; Figure 3 is a radar wave-absorbing performance graph of Example 1. DETAILED DESCRIPTION

[0016] The present application will be further described in conjunction with the examples: Example 1

[0017] (1) 71.84 g (1 mol) of ferrous oxide, 43.465 g (0.5 mol) of manganese oxide, 40.3 g (1 mol) of magnesium oxide, 159.08 g (2 mol) of copper oxide, 224.07 g (3 mol) of nickel oxide and 663.44 g (4 mol) of cobalt sesquioxide were used as raw materials, ball-mixed, dried, granulated and pressed into a green sheet; the green sheet was placed in a furnace and heat-treated at 1500℃ for 2h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and the results of the Needle algorithm optimization, the film system structure was designed, and the results are shown in Table 1.

[0018] Table 1 Material and thickness of each film layer Number of layers 1 2 3 4 5 6 7 8 9 Material MgF2 Ge [HfO2] Ge MgO Te Si TiO2 Ge Thickness / nm 3000 300 100 1500 2000 800 20 1000 1200 (3) Based on the above film system, MgF2 / Ge / HfO2 / MgO / Te / Si / TiO2 was used as the target material to deposit a film on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 0.01 Pa, gas flow rate 50 ml / min, and power 60 W. Finally, a multispectral suppression ceramic material compatible with laser-infrared-radar was obtained. Its laser protection performance is as follows: Figure 1 and 2 As shown, the reflectivity at characteristic laser points of 1.06, 1.54, and 10.6 µm can reach 2.19%, 1.78%, and 2.9%, respectively. Its infrared protection performance is as follows: Figure 2 As shown, its reflectivity can reach 97% in the infrared absorption bands of 3-5µm and 8-14µm. Its radar protection performance is as follows: Figure 3 As shown, it has an effective absorption bandwidth of 3.2 GHz and a minimum reflection loss of -67.4 dB with an ultra-thin thickness of 2.2 mm. Example 2

[0019] (1) Using 159.7g (1mol) ferric oxide, 283.76g (4mol) manganese oxide, 120.93g (3mol) magnesium oxide, 159.1g (2mol) copper oxide, 74.69g (1mol) nickel oxide and 82.93g (0.5mol) cobalt oxide as raw materials, the mixture was ball-milled and dried, then granulated and pressed into green sheets; the green sheets were placed in a furnace and kept at 800℃ for 12h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and Needle algorithm optimization results, the membrane structure was designed, and the results are shown in Table 2.

[0020] Table 2. Materials and thicknesses of each membrane layer Number of layers 1 2 3 4 5 6 7 8 9 Material MgO Te Si MgF2 Ge TiO2 Te [HfO2] Ge Thickness / nm 600 800 300 2000 1400 100 600 1800 300 (3) Based on the above membrane system, using MgF2 / Ge / HfO 2 / Using MgO / Te / Si / TiO2 as the target material, a film was deposited on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 3 Pa, gas flow rate 80 ml / min, and power 30 W, ultimately yielding a multispectral suppression ceramic material compatible with laser, infrared, and radar. Its laser protection performance is characterized by reflectivity of 3.17%, 2.16%, and 1.54% at characteristic laser points of 1.06, 1.54, and 10.6 µm, respectively. Its infrared protection performance is characterized by reflectivity reaching 95% in the 3-5 µm and 8-14 µm infrared absorption bands. Its radar protection performance is characterized by an effective absorption bandwidth of 3.3 GHz and a minimum reflection loss of -58.4 dB at an ultra-thin thickness of 2.1 mm. Example 3

[0021] (1) Using 231.55g (1mol) of iron(II,III) oxide, 212.82g (3mol) of manganese(II), 161.72g (4mol) of magnesium(II), 39.775g (0.5mol) of copper(II), 37.34g (0.5mol) of nickel(II) oxide and 331.72g (2mol) of cobalt(II) oxide as raw materials, the mixture was ball-milled and dried, then granulated and pressed into green sheets; the green sheets were placed in a furnace and kept at 1000℃ for 9h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and Needle algorithm optimization results, the membrane structure was designed, and the results are shown in Table 3.

[0022] Table 3. Materials and thicknesses of each membrane layer Number of layers 1 2 3 4 5 6 7 8 9 Material TiO2 Ge Si [HfO2] Ge MgF2 Te MgO Te Thickness / nm 2000 400 490 1000 900 500 1500 200 1000 (3) Based on the above film system, MgF2 / Ge / HfO2 / MgO / Te / Si / TiO2 was used as the target material to deposit a film on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 5 Pa, gas flow rate 5 ml / min and power 100 W. Finally, a multispectral suppression ceramic material compatible with laser-infrared-radar was obtained. Its laser protection performance is that the reflectivity at characteristic laser points of 1.06, 1.54 and 10.6 µm can reach 1.24%, 3.16% and 2.21%, respectively. Its infrared protection performance is that the reflectivity in the infrared absorption band of 3-5 µm and 8-14 µm can reach 96%. Its radar protection performance is that it has an effective absorption bandwidth of 3.1 GHz and a minimum reflection loss of -62.1 dB with an ultra-thin thickness of 2.3 mm. Example 4

[0023] (1) Using 71.84g (1mol) ferrous oxide, 141.88g (2mol) manganese oxide, 120.93g (3mol) magnesium oxide, 318.2g (4mol) copper oxide, 37.34g (0.5mol) nickel oxide and 331.72g (2mol) cobalt trioxide as raw materials, the mixture was ball-milled and dried, then granulated and pressed into green sheets; the green sheets were placed in a furnace and kept at 1300℃ for 4h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and Needle algorithm optimization results, the membrane structure was designed, and the results are shown in Table 4.

[0024] Table 4. Materials and thicknesses of each membrane layer Number of layers 1 2 3 4 5 6 7 8 9 Material [HfO2] Te TiO2 Ge MgF2 Ge Si MgO Te Thickness / nm 100 1200 800 300 2800 1000 400 3000 500 (3) Based on the above film system, MgF2 / Ge / HfO2 / MgO / Te / Si / TiO2 was used as the target material to deposit a film on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 8 Pa, gas flow rate 5 ml / min and power 200 W. Finally, a multispectral suppression ceramic material compatible with laser-infrared-radar was obtained. Its laser protection performance is that the reflectivity at characteristic laser points of 1.06, 1.54 and 10.6 µm can reach 2.17%, 1.45% and 1.52%, respectively. Its infrared protection performance is that the reflectivity in the infrared absorption band of 3-5 µm and 8-14 µm can reach 97%. Its radar protection performance is that it has an effective absorption bandwidth of 3.4 GHz and a minimum reflection loss of -57.1 dB with an ultra-thin thickness of 2.1 mm. Example 5

[0025] (1) Using 231.55g (1mol) of iron(II,III) oxide, 70.94g (1mol) of manganese(II), 80.62g (2mol) of magnesium(II), 238.65g (3mol) of copper(II), 298.76g (4mol) of nickel(II) oxide and 165.86g (1mol) of cobalt(II) oxide as raw materials, the mixture was ball-milled and dried, then granulated and pressed into green sheets; the green sheets were placed in a furnace and kept at 900℃ for 11h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and Needle algorithm optimization results, the membrane structure was designed, and the results are shown in Table 5.

[0026] Table 5. Materials and thicknesses of each membrane layer Number of layers 1 2 3 4 5 6 7 8 9 Material [HfO2] Te Si [HfO2] Ge MgF2 Te MgF2 Ge Thickness / nm 400 900 160 800 1200 2800 1400 1400 300 (3) Based on the above film system, MgF2 / Ge / HfO2 / MgO / Te / Si / TiO2 was used as the target material to deposit a film on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 10 Pa, gas flow rate 100 ml / min and power 150 W. Finally, a multispectral suppression ceramic material compatible with laser-infrared-radar was obtained. Its laser protection performance is that the reflectivity at characteristic laser points of 1.06, 1.54 and 10.6 µm can reach 1.25%, 2.98% and 2.53%, respectively. Its infrared protection performance is that the reflectivity in the infrared absorption bands of 3-5 µm and 8-14 µm can reach 95%. Its radar protection performance is that it has an effective absorption bandwidth of 3.1 GHz and a minimum reflection loss of -67.7 dB with an ultra-thin thickness of 2.3 mm. Example 6

[0027] (1) Using 159.7g (1mol) ferric oxide, 283.76g (4mol) manganese oxide, 20.15g (0.5mol) magnesium oxide, 238.65g (3mol) copper oxide, 149.38g (2mol) nickel oxide and 663.44g (4mol) cobalt oxide as raw materials, the mixture was ball-milled and dried, then granulated and pressed into green sheets; the green sheets were placed in a furnace and kept at 1100℃ for 7h to obtain a high-entropy ceramic substrate; (2) Based on the FDTD simulation design and Needle algorithm optimization results, the membrane structure was designed, and the results are shown in Table 6.

[0028] Table 6. Materials and thicknesses of each membrane layer Number of layers 1 2 3 4 5 6 7 8 9 Material MgF2 Ge Si TiO2 Ge TiO2 Te MgO Ge Thickness / nm 2000 1200 370 120 440 980 890 2700 1200 (3) Based on the above film system, MgF2 / Ge / HfO2 / MgO / Te / Si / TiO2 was used as the target material to deposit a film on a high-entropy ceramic substrate. The deposition parameters were: vacuum degree 0.5 Pa, gas flow rate 20 ml / min and power 300 W. Finally, a multispectral suppression ceramic material compatible with laser-infrared-radar was obtained. Its laser protection performance is that the reflectivity at characteristic laser points of 1.06, 1.54 and 10.6 µm can reach 3.12%, 2.45% and 1.86%, respectively. Its infrared protection performance is that the reflectivity in the infrared absorption band of 3-5 µm and 8-14 µm can reach 96%. Its radar protection performance is that it has an effective absorption bandwidth of 3.1 GHz and a minimum reflection loss of -62.2 dB with an ultra-thin thickness of 2.2 mm.

Claims

1. A method for preparing a laser-infrared-radar compatible multispectral suppression ceramic material, the specific steps of which are as follows: A. Preparation of high-entropy ceramic materials: using iron oxide, manganese oxide, magnesium oxide, copper oxide, nickel oxide and cobalt trioxide as raw materials, the materials are ball-milled, mixed evenly, dried, granulated and pressed into green sheets, and then calcined in a furnace to obtain a high-entropy ceramic substrate; B. Thin film deposition: Using a sputtering process, a low refractive index material L, a defect layer material S, and a high refractive index material H are deposited on the high-entropy ceramic substrate obtained in step A. By controlling the film thickness, vacuum level, gas flow rate, and sputtering power, a ceramic material with multispectral suppression performance compatible with laser-infrared-radar is obtained. The prepared film structure is: substrate|(LH)(LH)(LH)S(LH)|Air or substrate|(LH)S(LH)(LH)(LH)|Air.

2. The preparation method according to claim 1, characterized in that: The iron oxide is ferrous oxide, ferric oxide, or iron(II) oxide.

3. The preparation method according to claim 1, characterized in that: The molar ratio of iron oxide, manganese oxide, magnesium oxide, copper oxide, nickel oxide and cobalt trioxide is 1:(0.5-4):(0.5-4):(0.5-4):(0.5-4):(0.5-4):(0.5-4).

4. The preparation method according to claim 1, characterized in that: The calcination temperature is 800-1500℃, and the holding time is 2-12h.

5. The preparation method according to claim 1, characterized in that: The low refractive index material L is MgF2, MgO, TiO2 or HfO2; the defect layer material S is Si; and the high refractive index material H is Ge or Te.

6. The preparation method according to claim 1, characterized in that: The thickness of the film layer is as follows: 100-3000 nm for low refractive index material film layer; 300-1500 nm for high refractive index material film layer; and 20-500 nm for defect layer material.

7. The preparation method according to claim 1, characterized in that: The vacuum level is 0.01-10 Pa; the gas flow rate is 5-100 ml / min; and the sputtering power is 30-300 W.

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