A composite coating based on ultra-high temperature ceramic material and a method for producing and using the same

Abstract

The application provides a composite coating based on ultrahigh-temperature ceramic material and a preparation method and application thereof, and belongs to the technical field of coating materials. The low-emission solar energy absorption coating based on ultrahigh-temperature ceramic material is constructed through scientific and reasonable material design and advanced and precise preparation process, the ultrahigh-temperature ceramic material is innovatively introduced into the solar energy absorption coating system, the performance bottleneck of the traditional coating in the air environment application can be broken through, the high absorption rate, the low emission rate and the excellent thermal stability of the coating in the high-temperature air environment can be realized, and a solid material foundation for efficient and reliable utilization of solar energy in the high-temperature and complex air environment is laid.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating materials, and particularly relates to a composite coating based on ultrahigh-temperature ceramic material and a preparation method and application thereof. BACKGROUND

[0002] Solar thermal technology, as an effective way to convert solar energy into usable heat energy, has been widely used in solar thermal power generation, seawater desalination, industrial heating and regional heating, and other fields, providing important support for achieving low-carbon and green development of society.

[0003] Spectrum-selective absorbing coatings (SSACs) play a crucial role in solar thermal systems, and their performance directly determines the efficiency of the system. Ideal SSACs need to have special optical properties: in the main spectral range of solar radiation (0.3-2.5 μm), they should have extremely high absorption (greater than 0.9) to maximize the capture of solar photon energy, which is the basis for achieving high-efficiency photo-thermal conversion. In the mid-infrared-infrared region (2.5-20 μm), they should have a low emissivity (less than 0.3). In this waveband, if the coating has a high reflectivity, it means that a large amount of absorbed solar energy will be reflected back to the environment in the form of infrared radiation, which not only reduces the utilization efficiency of solar energy, but also leads to the waste of thermal energy. Low reflectivity can ensure that as much absorbed solar energy as possible is retained inside the coating and converted into useful heat energy, thereby significantly improving the photo-thermal conversion efficiency. At the same time, low emissivity can inhibit heat loss due to thermal radiation, allowing absorbed solar energy to be effectively stored in the system for a long time.

[0004] Currently, researchers have developed various types of spectrum-selective absorbing coatings by innovating material systems and carefully designing microstructures. In practical applications, SSACs are usually used in a vacuum environment. Vacuum environment can significantly reduce thermal conductivity and effectively reduce convective heat loss, providing ideal conditions for the coating to exhibit its high-efficiency photo-thermal conversion performance. In some high-precision solar experimental devices and space applications with strict requirements for heat loss, SSACs in a vacuum environment can work stably and efficiently.

[0005] However, the actual application scenarios are much more complex than the ideal conditions. Considering the possible accidental vacuum leakage, and in the application scenarios where the vacuum environment cannot be maintained, such as high-concentration solar tower receivers, long-term exposure to open air environment, it is particularly important to study the thermal stability of SSACs in air environment. In air, the coating faces more complex and demanding challenges, the presence of oxygen, water vapor and various corrosive gases can easily cause oxidation, corrosion and other problems of the coating, thereby destroying the coating structure and causing a sharp decline in its optical performance and thermal stability. Especially in high-temperature solar thermal utilization scenarios, such as solar tower power generation systems, the working temperature of the receiver is often as high as 700 DEG C or even higher. Under such high-temperature air environment, ordinary coatings are prone to performance deterioration in a short time, which seriously affects the power generation efficiency, increases the equipment maintenance cost and operation risk. SUMMARY

[0006] The purpose of the present application is to provide a composite coating based on ultra-high temperature ceramic material and its preparation method and application, which can achieve high absorption, low emission and excellent thermal stability in high-temperature air environment.

[0007] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0008] The present application provides a preparation method of a composite coating based on ultra-high temperature ceramic material, comprising the following steps:

[0009] A multi-arc ion plating film method is used, a titanium target is used as the target material, nitrogen is used to perform first sputtering on the surface of the substrate to form a titanium nitride infrared reflection layer;

[0010] A magnetron sputtering plating film method is used, hafnium carbide and hafnium boride are used as double targets, second sputtering is performed on the surface of the titanium nitride infrared reflection layer to form a hafnium carbide-hafnium boride composite ceramic absorption layer;

[0011] A magnetron sputtering plating film method is used, aluminum oxide is used as the target material, third sputtering is performed on the surface of the hafnium carbide-hafnium boride composite ceramic absorption layer to form an aluminum oxide anti-reflection layer;

[0012] The material obtained by the third sputtering is subjected to annealing treatment under air conditions to obtain a composite coating based on ultra-high temperature ceramic material.

[0013] Preferably, the conditions of the first sputtering include: vacuum degree (3.0-4.0) x 10 -3 Pa, titanium target current 145-155 A, nitrogen sputtering gas pressure 2-4 Pa, substrate direct current negative bias 50-55 V, and deposition time 115-130 min.

[0014] Preferably, the substrate comprises a stainless steel substrate or a nickel-based alloy steel substrate; the thickness of the titanium nitride infrared reflection layer is 4.9-5.5 microns.

[0015] Preferably, the second sputtering conditions comprise: vacuum degree (6.0-8.0) x 10 -4 Pa, argon flow rate 20-70 sccm, deposition time 30-33 min, hafnium carbide target power 3-6 W / cm 2 , hafnium boride target power 2-5 W / cm 2 .

[0016] Preferably, the thickness of the hafnium carbide-hafnium boride composite ceramic absorption layer is 50-60 nm.

[0017] Preferably, the third sputtering conditions comprise: vacuum degree (6.0-8.0) x 10 -4 Pa, argon flow rate 20-70 sccm, deposition time 115-125 min, aluminum oxide target power 2-4 W / cm 2 .

[0018] Preferably, the thickness of the aluminum oxide anti-reflection layer is 50-60 nm.

[0019] Preferably, the annealing treatment temperature is 195-205 DEG C, and the time is 115-125 min.

[0020] The application provides a composite coating based on ultra-high temperature ceramic material prepared by the preparation method.

[0021] The application provides application of the composite coating based on ultra-high temperature ceramic material in the field of spectrum selective absorption coating.

[0022] The application provides a preparation method of a composite coating based on ultra-high temperature ceramic material.

[0023] The preparation process of the application has the following advantages:

[0024] 1) The titanium nitride infrared reflection layer is prepared by multi-arc ion plating

[0025] Structural advantages: Multi-arc ion plating technology can make titanium nitride particles uniformly deposited on the substrate surface, forming a dense coating structure. Under given sputtering conditions, the growth of titanium nitride can be precisely controlled to obtain good crystal orientation, which is beneficial to improve the density and integrity of the coating.

[0026] Performance effect: The vacuum degree, titanium target current, nitrogen sputtering gas pressure, substrate DC negative bias and deposition time, etc. jointly act on the titanium nitride infrared reflection layer to make it have high infrared reflectivity, effectively reflect infrared light in the infrared band, reduce heat absorption, and at the same time, it is firmly combined with the substrate, has good mechanical properties and chemical stability.

[0027] 2) Use magnetic control sputtering to prepare hafnium carbide-hafnium boride composite ceramic absorption layer

[0028] Structural advantages: Through double-target co-sputtering technology, the deposition ratio and rate of hafnium carbide and hafnium boride can be precisely controlled to form a uniform, dense and composition-controllable composite ceramic absorption layer on the substrate. Under given sputtering conditions, nanoscale grain size and fine microstructure can be obtained, which is beneficial to improve the optical absorption performance of the absorption layer.

[0029] Performance effect: Lower vacuum degree, appropriate argon flow rate, and specific target power and deposition time make the hafnium carbide-hafnium boride composite ceramic absorption layer have high absorption rate for visible light and near-infrared light in the solar spectrum, effectively absorb solar radiation energy, and at the same time have good high-temperature resistance and chemical stability, can maintain stable performance in high-temperature environment.

[0030] 3) Use magnetic control sputtering to prepare aluminum oxide anti-reflection layer

[0031] Structural advantages: Under given sputtering conditions, the aluminum oxide anti-reflection layer has uniform thickness and good optical flatness, its microstructure is dense and has no obvious defects, and it can be well combined with the underlying hafnium carbide-hafnium boride composite ceramic absorption layer and the upper titanium nitride infrared reflection layer to form a stable multilayer structure.

[0032] Performance effect: The aluminum oxide anti-reflection layer can reduce the reflectivity of the coating surface, increase the transmittance of solar radiation, so that more light can enter the hafnium carbide-hafnium boride composite ceramic absorption layer and be absorbed, thereby improving the solar absorption efficiency of the entire coating, and at the same time, it can also play a protective role for the underlying absorption layer and reflection layer, improving the weather resistance and chemical stability of the coating.

[0033] 4) Annealing treatment

[0034] Structural advantages: annealing treatment can make the grains in the coating further grow and perfect, reduce the lattice defects, improve the crystalline quality and structural stability of the coating. Under the condition of air, with a certain heating rate and annealing temperature, a stable oxide layer is formed on the surface of the coating, which improves the oxidation resistance of the coating.

[0035] Performance effect: annealing treatment can improve the optical performance of the coating, make the interface between the layers more closely, improve the overall mechanical properties and stability of the coating, and help the coating maintain good solar spectrum selective absorption performance during long-term use.

[0036] The contribution of each layer of ceramic material prepared by the present application to the selective absorption of solar spectrum is:

[0037] 1) Titanium nitride infrared reflection layer: the main contribution is to reflect the infrared light in the solar spectrum. Titanium nitride has high infrared reflectivity, which can reflect most of the infrared light and reduce the absorption of infrared light, thereby reducing the absorption rate of the coating in the infrared band, improving the spectral selectivity of the coating, and minimizing the absorption of infrared light while absorbing visible light, reducing the heat loss of the coating.

[0038] 2) Hafnium carbide-hafnium boride composite ceramic absorption layer: it is the main functional layer of solar spectrum selective absorption. Hafnium carbide and hafnium boride have unique optical absorption characteristics, with high absorption rate for visible light and near-infrared light, which can absorb most of the visible light and near-infrared light in solar radiation and convert it into heat energy, thereby improving the absorption efficiency of the coating to solar energy, and is the key layer to achieve high absorption rate of the coating.

[0039] 3) Alumina anti-reflection layer: it has little contribution to the absorption of solar spectrum, but it can reduce the reflectivity of the coating surface, increase the transmittance of light in each band of solar spectrum into the coating, and make more light reach the hafnium carbide-hafnium boride composite ceramic absorption layer to be absorbed, thereby indirectly improving the absorption efficiency of the coating to solar energy, and also improving the optical performance of the coating, making the coating have better spectral selectivity.

[0040] The present application uses titanium nitride infrared reflection layer, hafnium carbide-hafnium boride composite ceramic absorption layer and alumina anti-reflection layer to construct a composite coating, which has the following synergistic effects:

[0041] High solar absorption efficiency: the hafnium carbide-hafnium boride composite ceramic absorption layer is responsible for absorbing most of the visible light and near-infrared light, the titanium nitride infrared reflection layer reflects the infrared light to reduce heat loss, and the alumina anti-reflection layer improves the light transmittance, so that more light is absorbed by the absorption layer. The three work together to achieve high-efficiency absorption of solar energy by the coating, thereby improving the solar absorption efficiency.

[0042] Good spectral selectivity: the titanium nitride infrared reflection layer reduces the infrared absorption rate, the hafnium carbide-hafnium boride composite ceramic absorption layer increases the visible light and near-infrared light absorption rate, and the alumina anti-reflection layer optimizes the optical performance. The three layers work together to make the coating have good selectivity in the entire solar spectrum range, can selectively absorb visible light and near-infrared light, and reflect infrared light, thereby improving the photo-thermal conversion efficiency of the coating.

[0043] Excellent stability and durability: the titanium nitride infrared reflection layer, the hafnium carbide-hafnium boride composite ceramic absorption layer and the alumina anti-reflection layer each have good chemical stability and mechanical properties, and the three layers are combined tightly to form a stable multilayer structure. Annealing treatment further improves the crystalline quality and interface bonding strength of the coating, so that the coating has excellent stability and durability, and can maintain good solar spectral selective absorption performance in the long-term use process and resist the erosion and damage of the external environment. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 Structure schematic diagram of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared for Example 1, wherein 1 is a substrate, 2 is a titanium nitride infrared reflection layer, 3 is a hafnium carbide-hafnium boride composite ceramic absorption layer, and 4 is an alumina anti-reflection layer;

[0045] Figure 2 Reflection spectrum of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared for Example 1;

[0046] Figure 3 Reflection spectrum of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared for Example 1 after annealing at 500℃ for 10h;

[0047] Figure 4 TEM diagram of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared for Example 1. DETAILED DESCRIPTION

[0048] In the present application, the required raw materials or reagents are all commercially available goods well known to those skilled in the art, unless otherwise specified.

[0049] The present application provides a preparation method of a composite coating based on ultrahigh-temperature ceramic materials, comprising the following steps:

[0050] A multi-arc ion plating film method is adopted, a titanium target is used as the target material, nitrogen is used to perform first sputtering on the surface of the substrate, and a titanium nitride infrared reflection layer is formed.

[0051] The second sputtering is performed on the surface of the titanium nitride infrared reflection layer by using a magnetron sputtering film method and taking hafnium carbide and hafnium boride as double targets to form a hafnium carbide-hafnium boride composite ceramic absorption layer;

[0052] The third sputtering is performed on the surface of the hafnium carbide-hafnium boride composite ceramic absorption layer by using a magnetron sputtering film method and taking aluminum oxide as a target material to form an aluminum oxide anti-reflection layer;

[0053] The material obtained by the third sputtering is subjected to annealing treatment in air to obtain a composite coating based on ultra-high temperature ceramic material.

[0054] In the present application, the conditions of the first sputtering preferably include: vacuum degree (3.0-4.0) × 10 -3 Pa, titanium target current 145-155 A, nitrogen sputtering gas pressure 2-4 Pa, substrate direct current negative bias 50-55 V, and deposition time 115-130 min, and more preferably: vacuum degree 4.0 × 10 -3 Pa, titanium target current 150 A, nitrogen sputtering gas pressure 3-4 Pa, substrate direct current negative bias 50 V, and deposition time 2 h.

[0055] In the present application, the substrate preferably includes a stainless steel substrate or a nickel-based alloy steel substrate; the stainless steel substrate is preferably 316 stainless steel or 304 stainless steel; the present application does not have special limitations on the specific specifications and sources of the substrate, and commercially available products known in the art can be used.

[0056] In the present application, the thickness of the titanium nitride infrared reflection layer is preferably 4.9-5.5 μm, and more preferably 5-5.3 μm.

[0057] In the present application, the conditions of the second sputtering preferably include: vacuum degree (6.0-8.0) × 10 -4 Pa, argon flow rate 20-70 sccm, deposition time 30-33 min, hafnium carbide target power 3-6 W / cm 2 , hafnium boride target power 2-5 W / cm 2 , and more preferably: vacuum degree 8.0 × 10 -4 Pa, argon flow rate 28 sccm, deposition time 32 min, hafnium carbide target power 5-5.49 W / cm 2 , and hafnium boride target power 3.29-4 W / cm 2 .

[0058] In the present application, the thickness of the hafnium carbide-hafnium boride composite ceramic absorption layer is preferably 50-60 nm, and more preferably 55-58.6 nm.

[0059] In the present application, the conditions of the third sputtering preferably include: vacuum degree (6.0-8.0) × 10-4 Pa, argon flow rate 20-70sccm, deposition time 115-125min, alumina target material power 2-4W / cm 2 ; more preferably: vacuum degree (7.0-8.0) x 10 -4 Pa, argon flow rate 28-40sccm, deposition time 2h, alumina target material power 3-3.29W / cm 2 .

[0060] In the present application, the thickness of the alumina antireflection layer is preferably 50-60nm, more preferably 52.6-55nm.

[0061] In the present application, the temperature of the annealing treatment is preferably 195-205℃, more preferably 200℃, and the time is preferably 115-125min, more preferably 120min.

[0062] The present application does not have special limitations on the specific source of the target material used in the first sputtering, second sputtering and third sputtering, and commercially available products with a purity of ≥99.99% known in the art can be used.

[0063] The present application does not have special limitations on the specific operation process of the first sputtering, second sputtering and third sputtering, and known processes in the art can be used.

[0064] The present application provides a composite coating based on ultra-high temperature ceramic material prepared by the preparation method described in the above technical solution.

[0065] The present application provides an application of the composite coating based on ultra-high temperature ceramic material described in the above technical solution in the field of spectrally selective absorption coating.

[0066] The present application does not have special limitations on the method of the application, and the composite coating can be used as a spectrally selective absorption coating according to the method known in the art.

[0067] The specific embodiments of the present application are described in detail below, but it should be understood that the protection scope of the present application is not limited by the specific embodiments. Based on the examples in the present application, all other examples obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present application. The experimental methods described in the embodiments of the present application are conventional methods unless otherwise specified.

[0068] The experimental methods and detection methods described below are conventional methods unless otherwise specified; the reagents and raw materials described below are commercially available unless otherwise specified.

[0069] Example 1

[0070] The preparation method of the composite coating based on ultra-high temperature ceramic material in the embodiment is as follows:

[0071] Substrate: 316 polished stainless steel substrate SS;

[0072] The multi-arc ion plating film technology was adopted, the titanium target was used as the target material, nitrogen was used for the first sputtering on the surface of the substrate, the sputtering condition was that the vacuum degree was 4.0*10 -3 Pa, the titanium target current was 150 A, the nitrogen sputtering gas pressure was 4 Pa, the substrate direct current negative bias voltage was 50 V, and the deposition time was 2 h, so that a titanium nitride infrared reflection layer with a thickness of 5 μm was formed on the surface of the substrate;

[0073] The magnetron sputtering film technology was adopted, hafnium carbide and hafnium boride double targets were co-sputtered, the sputtering condition was that the vacuum degree was 8.0*10 -4 Pa, the argon flow rate was 28 sccm, the deposition time was 32 min, the hafnium carbide target material power was 5.49 W / cm 2 , the hafnium boride target material power was 3.29 W / cm 2 , and a hafnium carbide-hafnium boride composite ceramic absorption layer with a thickness of 58.6 nm was formed;

[0074] The magnetron sputtering film technology was adopted, and aluminum oxide was used as the target material for sputtering, the sputtering condition was that the vacuum degree was 8.0*10 - 4 Pa, the argon flow rate was 28 sccm, the deposition time was 2 h, the aluminum oxide target material power was 3.29 W / cm 2 , and an aluminum oxide anti-reflection layer with a thickness of 52.6 nm was formed;

[0075] The obtained coating material was annealed at 200 DEG C for 120 min in air, and a composite coating based on ultra-high temperature ceramic material was obtained, which was recorded as SS / TiN / HfC-HfB2 / Al2O3 composite coating, and the schematic diagram of the layer structure is shown in Figure 1 .

[0076] Example 2

[0077] The preparation method of the composite coating based on ultra-high temperature ceramic material in the embodiment is as follows:

[0078] Substrate: 304 polished stainless steel substrate;

[0079] The multi-arc ion plating film technology was adopted, the titanium target was used as the target material, nitrogen was used for the first sputtering on the surface of the substrate, the sputtering condition was that the vacuum degree was 3.0*10 -3 Pa, the titanium target current was 145 A, the nitrogen sputtering gas pressure was 3 Pa, the substrate direct current negative bias voltage was 50 V, and the deposition time was 115 min, so that a titanium nitride infrared reflection layer with a thickness of 4.9 μm was formed on the surface of the substrate;

[0080] The carbonized hafnium and boronized hafnium double targets are co-sputtered by the magnetron sputtering coating technology, the sputtering conditions are as follows: vacuum degree 6.0*10 -4 Pa, argon flow rate 20sccm, deposition time 30min, carbonized hafnium target power 3W / cm 2 , boronized hafnium target power 2W / cm 2 , to form a carbonized hafnium-boronized hafnium composite ceramic absorption layer with a thickness of 50nm;

[0081] The aluminum oxide is sputtered by the magnetron sputtering coating technology, the sputtering conditions are as follows: vacuum degree 6.0*10 - 4 Pa, argon flow rate 20sccm, deposition time 115min, aluminum oxide target power 2W / cm 2 , to form an aluminum oxide anti-reflection layer with a thickness of 50nm;

[0082] The obtained coating material is annealed at 200℃ in air for 120min at a heating rate of 5℃ / min, to obtain a composite coating based on ultra-high temperature ceramic material, with an absorption rate of 90% and an emissivity of 5%.

[0083] Example 3

[0084] The preparation method of the composite coating based on ultra-high temperature ceramic material in this embodiment is as follows:

[0085] Substrate: 304 polished stainless steel substrate;

[0086] The titanium target is used as the target material by the multi-arc ion plating coating technology, and the nitrogen gas is used for the first sputtering on the surface of the substrate, the sputtering conditions are as follows: vacuum degree 4.0*10 -3 Pa, titanium target current 155A, nitrogen sputtering pressure 4Pa, substrate direct current negative bias voltage 55V, deposition time 130min, to form a titanium nitride infrared reflection layer with a thickness of 5.5μm on the surface of the substrate;

[0087] The carbonized hafnium and boronized hafnium double targets are co-sputtered by the magnetron sputtering coating technology, the sputtering conditions are as follows: vacuum degree 8.0*10 -4 Pa, argon flow rate 70sccm, deposition time 33min, carbonized hafnium target power 6W / cm 2 , boronized hafnium target power 5W / cm 2 , to form a carbonized hafnium-boronized hafnium composite ceramic absorption layer with a thickness of 60nm;

[0088] The aluminum oxide is sputtered by the magnetron sputtering coating technology, the sputtering conditions are as follows: vacuum degree 8.0*10 - 4 Pa, argon flow rate 70sccm, deposition time 125min, aluminum oxide target power 4W / cm 2An aluminum oxide antireflective layer with a thickness of 60 nm is formed.

[0089] The obtained coating material was annealed at 200°C for 120 min under air conditions to obtain a composite coating based on ultra-high temperature ceramic material with an absorptivity of 90% and an emissivity of 4%.

[0090] Example 4

[0091] The preparation method of the composite coating based on ultra-high temperature ceramic materials in this embodiment is as follows:

[0092] Substrate: Nickel-based alloy steel Incoloy 800 substrate;

[0093] Multi-arc ion plating technology was employed, using a titanium target as the target material. Nitrogen gas was used for the first sputtering on the substrate surface. The sputtering conditions were: vacuum degree 3.5 × 10⁻⁶. -3 Pa, titanium target current 150A, nitrogen sputtering pressure 3.5Pa, substrate DC negative bias voltage 50V, deposition time 120min, forming a titanium nitride infrared reflective layer with a thickness of 5.3μm on the substrate surface;

[0094] Magnetron sputtering deposition technology was employed, using a dual-target co-sputtering system of hafnium carbide and hafnium boride. Sputtering conditions: vacuum degree 7.0 × 10⁻⁶. -4 Pa, argon flow rate 40 sccm, deposition time 30 min, hafnium carbide target power 5 W / cm² 2 Hafnium boride target power 4W / cm 2 A hafnium carbide-hafnium boride composite ceramic absorber layer with a thickness of 55 nm is formed.

[0095] Magnetron sputtering deposition technology was employed, using alumina as the target material. Sputtering conditions: vacuum degree 7.0 × 10⁻⁶. - 4 Pa, argon flow rate 40 sccm, deposition time 120 min, alumina target power 3 W / cm 2 An aluminum oxide antireflective layer with a thickness of 55 nm is formed.

[0096] The obtained coating material was annealed at 200°C for 120 min under air conditions to obtain a composite coating based on ultra-high temperature ceramic material with an absorptivity of 90% and an emissivity of 4%.

[0097] Performance testing

[0098] 1) Coating spectral selectivity:

[0099] Figure 2 The reflectance spectrum of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared in Example 1; Figure 2 It can be seen that the composite coating has an absorption rate of 91% and an emissivity of 3%.

[0100] 2) Coating thermal stability:

[0101] The composite coating prepared in Example 1 was annealed at 500℃ for 10h under air condition with a heating rate of 5℃ / min, and its emission spectrum was tested, and the result is shown in Figure 3 .

[0102] Figure 3 The reflection spectrum of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared in Example 1 after annealing at 500℃ for 10h; it can be seen from Figure 3 that the absorption rate of the coating is 91% and the emission rate is 5% after annealing at 500℃ for 10h, the absorption rate is unchanged, the emission rate is slightly increased, and both the absorption rate and the emission rate have no obvious change, which indicates that the composite coating has excellent stability at 500℃.

[0103] 3) Figure 4 The TEM image of the SS / TiN / HfC-HfB2 / Al2O3 composite coating prepared in Example 1; as shown in Figure 4 , from top to bottom, it is the Al2O3 antireflection layer prepared by magnetron sputtering, the HfC-HfB2 layer prepared by magnetron sputtering, and the TiN infrared reflection layer prepared by multi-arc ion plating. Since the thickness of the TiN infrared reflection layer is large, only a part is shown.

[0104] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for producing a composite coating based on ultra-high temperature ceramic material, characterized in that The method comprises the following steps: A first sputtering is performed on the surface of the substrate by multi-arc ion plating method using a titanium target as the target material and nitrogen as the sputtering gas to form a titanium nitride infrared reflection layer; A second sputtering is performed on the surface of the titanium nitride infrared reflection layer by magnetron sputtering plating method using hafnium carbide and hafnium boride as double targets to form a hafnium carbide-hafnium boride composite ceramic absorption layer; A third sputtering is performed on the surface of the hafnium carbide-hafnium boride composite ceramic absorption layer by magnetron sputtering plating method using an aluminum oxide target as the target material to form an aluminum oxide anti-reflection layer; The material obtained by the third sputtering is subjected to an annealing treatment in air to obtain a composite coating based on ultra-high temperature ceramic material; The second sputtering condition includes: vacuum degree (6.0~8.0)×10 -4 Pa, argon flow rate 20~70sccm, deposition time 30~33min, hafnium carbide target power 3~6W / cm 2 , hafnium boride target power 2~5W / cm 2 .

2. The production method according to claim 1, characterized by, The first sputtering conditions include: vacuum degree (3.0~4.0)×10 -3 Pa, titanium target current 145~155 A, nitrogen sputtering gas pressure 2~4 Pa, substrate direct current negative bias 50~55 V, and deposition time 115~130 min.

3. The production method according to claim 1 or 2, characterized by, The substrate comprises a stainless steel substrate or a nickel-based alloy steel substrate; the thickness of the titanium nitride infrared reflection layer is 4.9-5.5 μm.

4. The method of claim 1, wherein, The thickness of the hafnium carbide-hafnium boride composite ceramic absorption layer is 50-60 nm.

5. The preparation method according to claim 1, characterized in that, The third sputtering condition includes: vacuum degree (6.0~8.0)×10 -4 Pa, argon flow rate 20~70sccm, deposition time 115~125min, aluminum oxide target material power 2~4W / cm 2 .

6. The production method according to claim 1 or 5, characterized by, The thickness of the aluminum oxide anti-reflection layer is 50-60 nm.

7. The preparation method according to claim 1, characterized in that, The annealing treatment is performed at a temperature of 195-205 ℃ for 115-125 min.

8. The composite coating based on ultra-high temperature ceramic material prepared by the preparation method of any one of claims 1-7.

9. The application of the composite coating based on ultra-high temperature ceramic material of claim 8 in the field of spectrally selective absorption coating.

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