CN106966764B - High-temperature oxidation-resistant composite coating of thermal structure composite material and preparation method thereof - Google Patents

High-temperature oxidation-resistant composite coating of thermal structure composite material and preparation method thereof Download PDF

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CN106966764B
CN106966764B CN201610412082.XA CN201610412082A CN106966764B CN 106966764 B CN106966764 B CN 106966764B CN 201610412082 A CN201610412082 A CN 201610412082A CN 106966764 B CN106966764 B CN 106966764B
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CN106966764A (en
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罗瑞盈
茅振国
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Beijing University of Aeronautics and Astronautics
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

Abstract

The invention relates to a high-temperature oxidation-resistant composite coating of a thermostructural composite material and a preparation method thereof. The preparation method of the high-temperature anti-oxidation composite coating of the thermostructural composite material comprises the following steps: preserving the heat of the thermostructural composite material for a first preset time at a first preset temperature, pre-oxidizing, and naturally cooling to room temperature; embedding the thermostructural composite material into the embedded powder under a protective atmosphere, and preserving heat for a second preset time at a second preset temperature to obtain the thermostructural composite material with the SiC coating; spraying the spraying powder on the thermal structure composite material with the SiC coating by adopting a plasma spraying method under the preset voltage and the preset current to prepare Si-Yb2Si2O7‑ZrB2And (4) coating. The preparation method of the high-temperature antioxidant composite coating of the thermostructural composite material has the advantages of simple preparation process, convenient operation, easily obtained raw materials and lower preparation cost.

Description

High-temperature oxidation-resistant composite coating of thermal structure composite material and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to a high-temperature oxidation-resistant composite coating of a thermostructure composite material and a preparation method thereof.
Background
Thermostructural composites are composites that have mechanical properties that make them suitable for use in constructing structural elements and have the ability to maintain these properties at high temperatures. Such thermostructural materials are in particular composed of carbon/carbon (C/C) composite materials (carbon fiber reinforcement and carbon matrix), as well as of ceramic matrix composite materials, such as C/SiC materials (carbon fiber reinforcement with a silicon carbide matrix), C/C-SiC materials (carbon fiber reinforcement with a carbon and silicon carbide mixed matrix), or even SiC/SiC materials.
Thermostructural composite materials have excellent high temperature physical properties, such as low density, high specific strength, low coefficient of thermal expansion, thermal shock resistance, and the like, making it useful in a wide variety of aerospace applications, such as rocket heat shields, the nose wings of space shuttles, and some heat resistant structural components of aircraft. The thermostructural composite material can keep stable and moderately improved mechanical property at the temperature of more than 2000 ℃ in an inert gas atmosphere, but starts to be rapidly oxidized at the temperature of 500 ℃ in an oxidizing atmosphere, so that the application of the thermostructural composite material in a high-temperature oxidizing environment is limited. Therefore, it is very important to solve the problem of oxidation resistance of the thermostructural composite material. There are two approaches to oxidation resistance of thermostructural composite materials: one is a composite material in thermal structureAn anti-oxidation material is added into the material matrix to improve the anti-oxidation capability of the matrix; the other method is to prepare an anti-oxidation coating on the surface of the thermostructural composite material to isolate air. The oxidation resistant coating technology can effectively solve the problem of oxidation of the thermal structure composite material on the premise of not influencing the mechanical property of the matrix, and is an optimal oxidation resistant way. Currently, ZrC, ZrB2、Hf(Zr)C、SiC、ZrC-SiC、ZrB2-SiC、Al2O3And mullite and other ceramic coatings are used for preparing the oxidation-resistant coating of the thermostructural composite material, so that the oxidation resistance of the thermostructural composite material can be effectively improved. Wherein, SiC/Si-MoSi prepared by northwest industry university and Shanxi science and technology university2-CrSi2Coating, SiC/SiC-ZrB2Coatings and the like all have good oxidation resistance. But the surface of the coating still generates cracks after long-time oxidation, so that the coating fails.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the invention aims to provide the preparation method of the high-temperature antioxidant composite coating of the thermostructural composite material, which has the advantages of simple preparation process, convenient operation, easily obtained raw materials and lower preparation cost.
The preparation method of the high-temperature anti-oxidation composite coating of the thermostructural composite material according to the embodiment of the invention comprises the following steps: pre-oxidation: preserving the heat of the thermostructural composite material for a first preset time at a first preset temperature, and naturally cooling the thermostructural composite material to room temperature after preoxidation; preparing a SiC coating: embedding the thermostructural composite material into the embedded powder under a protective atmosphere, and preserving heat for a second preset time at a second preset temperature to obtain the thermostructural composite material with the SiC coating; preparation of Si-Yb2Si2O7-ZrB2Coating: spraying the spraying powder on the thermal structure composite material with the SiC coating by adopting a plasma spraying method under the preset voltage and the preset current to prepare Si-Yb2Si2O7-ZrB2Coating; wherein the embedded powder at least comprises Si powder, C powder and Al powder2O3Pulverizing; the powder for spraying at least comprises Yb2Si2O7Powder ZrB2Powder, and Si powder.
According to the preparation method of the high-temperature anti-oxidation composite coating of the thermostructural composite material, disclosed by the embodiment of the invention, the powder can be heated to a molten or semi-molten state by a plasma spraying method and is sprayed to the surface of the substrate at a high speed to form the coating, so that the efficiency is high, the dimensional precision is controllable, the coating thickness is uniform, and the thermal damage to the substrate is small. ZrB2The medium Zr and B atom form strong covalent bond and metal bond, thus having high hardness and high temperature stability. Yb of2Si2O7The thermal expansion coefficient of the coating is small, the coating has extremely low oxygen permeability and water vapor permeability, and the environmental barrier performance of the coating is enhanced while the oxidation resistance of the thermostructural composite material is improved. After long-time high-temperature oxidation, the oxidation-resistant coating can be divided into three layers: unreacted layer of SiO2A glass layer and a Zr-Si-O glass layer. ZrO (ZrO)2The melting point of the glass reaches 2700 ℃, the volatilization at high temperature is little, the glass is very stable, and the Zr-Si-O glass layer and the SiO2The glass layer separates and covers it, has greater viscosity and lower oxygen permeability, and is more effective at providing antioxidant protection at 1600 ℃. The preparation method of the high-temperature antioxidant composite coating of the thermostructural composite material according to the embodiment of the invention has the advantages of simple preparation process, convenient operation, easily obtained raw materials and lower preparation cost.
In addition, the preparation method of the thermostructural composite material high-temperature oxidation-resistant composite coating according to the embodiment of the invention may further have the following additional technical features:
further, in the spray powder, Yb2Si2O720-36% of powder by weight and ZrB2The weight ratio of the powder is 26-40%, and the weight ratio of the Si powder is 30-48%.
Furthermore, in the embedding powder, the weight ratio of Si powder is 65-80%, the weight ratio of C powder is 10-25%, and Al powder2O3The weight ratio of the powder is 5-15%, the second preset temperature is 1800-2000 ℃, and the second preset time is 1-3 h.
Further, the preset voltage is 385V-425V, and the preset current is 115A-140A.
Further, the first preset temperature is 900-1000 ℃, and the first preset time is 3-6 min.
Furthermore, in the embedded powder material, the grain diameter of Si powder is 20-30 μm, the grain diameter of C powder is 20-30 μm, and Al powder2O3The particle size of the powder is 20-30 μm.
Further, Si-Yb is prepared in step2Si2O7-ZrB2In the coating, the spraying speed is 15 g/min-25 g/min, and the spraying distance is 80 mm-100 mm.
Further, before the pre-oxidation step, the method also comprises the following pretreatment steps: polishing the surface of the ultra-high temperature composite material, cleaning and drying at the drying temperature of 110-130 ℃ for 10-20 h.
Another object of the present invention is to provide a thermostructural composite material high temperature oxidation resistant composite coating.
The high-temperature oxidation-resistant composite coating of the thermostructural composite material according to the present invention comprises: a thermostructural composite material; a SiC coating covering the thermostructural composite material; Si-Yb2Si2O7-ZrB2Coating of Si-Yb2Si2O7-ZrB2The coating covers the SiC coating.
Further, Si-Yb2Si2O7-ZrB2The thickness of the coating is 90-110 μm.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a flow chart of a preparation method of a thermostructural composite material high-temperature oxidation-resistant composite coating according to an embodiment of the invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The preparation method of the thermostructural composite material high-temperature oxidation-resistant composite coating according to the embodiment of the invention mainly comprises the following steps.
Pre-oxidation: and (3) preserving the heat of the thermostructural composite material for a first preset time at a first preset temperature, and naturally cooling the thermostructural composite material to room temperature after preoxidation. Specifically, the cleaned thermostructural composite material is put into a quartz tube or a crucible with through holes at two ends, the quartz tube or the crucible is placed in a muffle furnace, a tube body is partially arranged in a constant temperature area in the middle of the furnace chamber, the temperature is raised to about 900-1000 ℃, the temperature is kept for about 3-6 min, the quartz tube is taken out from the furnace chamber of the muffle furnace after reaching the pre-oxidation time, and the quartz tube is naturally cooled in a room temperature environment. After the thermostructural composite material is pre-oxidized for 3-6 min at 900-1000 ℃, the interface bonding force of the coating and the matrix is obviously improved, and the problem that the thermal expansion coefficients of the coating substance and the matrix are not matched is effectively relieved, so that the cracking and falling tendency of the coating when a coating sample is used in a high-temperature and low-temperature alternating environment is weakened, and the oxidation resistance and the mechanical property of the coating sample are obviously improved.
Preparing a SiC coating: and embedding the thermostructural composite material into the embedded powder under a protective atmosphere, and preserving heat for a second preset time at a second preset temperature to obtain the thermostructural composite material with the SiC coating. Wherein the embedded powder at least comprises Si powder, C powder and Al powder2O3Powder, and Si powder, C powder and Al2O3The powder is 20-30 μm. Wherein, the weight ratio of Si powder is about 65-80%, the weight ratio of C powder is about 10-25%, and Al powder2O3The weight ratio of the powder is about 5-15%. The second preset temperature is about 1800-2000 ℃, and the second preset time is about 1-3 h. Specifically, according to 65-80% of Si powder, 10-25% of C powder and Al2O3Uniformly mixing 5-15% of powder by mass ratio, putting the powder into a graphite crucible as embedding powder, putting the crucible into a high-temperature vacuum graphitization furnace, preserving the heat for 1-3 h at 1800-2000 ℃ under the protection of argon gas, preparing a SiC coating on the surface of the thermostructural composite material, polishing the SiC coating by using sand paper to flatten the surface of the coating, and cleaning and drying the coating.
Preparation of Si-Yb2Si2O7-ZrB2Coating: using plasmaSpraying the spraying powder onto the thermal structure composite material with SiC coating by a body spraying method under the preset voltage and current to prepare Si-Yb2Si2O7-ZrB2And (4) coating. Wherein the spraying powder at least comprises Yb2Si2O7Powder ZrB2Powder and Si powder, and Yb2Si2O7Powder ZrB2The grain diameters of the powder and the Si powder are both 20-40 mu m. Wherein Yb2Si2O7The weight ratio of the powder is about 20 to 36 percent, ZrB2The weight ratio of the powder is 26-40%, and the weight ratio of the Si powder is about 30-48%. The preset voltage is 385-425V, and the preset current is 115-140A. In particular in terms of Yb2Si2O7The weight ratio of the powder is about 20 to 36 percent, ZrB2The weight ratio of the powder is 26-40%, the weight ratio of the Si powder is about 30-48%, 8-15 wt% of PVA solution is added after mixing, the concentration of the PVA solution is about 6-8 wt%, uniform slurry is obtained by ball milling with a ball mill, and the spherical powder is prepared by spray drying. Fixing a thermostructural composite material sample with a SiC inner coating on a spraying platform, and filling spraying powder into a powder feeder; spraying the spray powder onto the surface of the sample by a supersonic plasma spraying device, and repeatedly spraying, wherein the spraying thickness is about 3-5 μm each time, and the final spraying thickness is about 90-110 μm, so as to obtain the surface prepared with Si-Yb2Si2O7-ZrB2A thermostructural composite of coatings. After long-time high-temperature oxidation, the oxidation-resistant coating can be divided into three layers: unreacted layer of SiO2A glass layer and a Zr-Si-O glass layer. Zr-Si-O glass layer and SiO2The glass layer separates and covers it, has greater viscosity and lower oxygen permeability, and is more effective in providing antioxidant protection. At the same time, Yb2Si2O7The thermal expansion coefficient is small, the oxygen permeability and the water vapor permeability are extremely low, the oxidation resistance of the thermal structure composite material is improved, and the environmental barrier performance of the coating is enhanced.
The present invention will be described in detail with reference to specific examples.
Example one
Taking out the sample with the density of 1.75g/cm3The thermostructural composite material of (1) is processed into a sample of 10mm multiplied by 10mm, is polished by SiC sand paper, and is ultrasonically cleaned in absolute ethyl alcohol for 15 min; and drying the cleaned thermostructural composite material sample at the temperature of 120 ℃ for 15h for later use.
Putting the cleaned sample of the thermal structure composite material into a quartz tube with through holes at two ends, heating a muffle furnace by a program temperature control device, setting the pre-oxidation temperature to 900 ℃, putting the quartz tube filled with the thermal structure composite material into the muffle furnace when the temperature of the muffle furnace is increased to 900 ℃ and is constant, putting the tube body part filled with the sample into the middle of a furnace chamber, namely a constant temperature area, and ensuring that the pre-oxidation temperature of the sample is 900 ℃ and the pre-oxidation time is 3 min. And taking the quartz tube out of the muffle furnace chamber after the pre-oxidation time is reached, placing the quartz tube on a platform in a room temperature environment, naturally cooling the sample to room temperature, and weighing for later use.
Mixing Si powder, C powder and Al powder2O3Uniformly mixing the powder according to the mass ratio of 80%, 15% and 5%, putting the powder into a graphite crucible as embedding powder, putting the crucible into a high-temperature vacuum graphitization furnace, preserving the heat for 2 hours at 1800-2000 ℃ under the protection of argon gas, preparing a SiC coating on the surface of the thermostructural composite material, polishing the SiC coating by using sand paper to flatten the surface of the coating, and cleaning and drying the coating.
Preparation of Si-Yb by plasma spraying2Si2O7-ZrB2And (4) an anti-oxidation coating. Firstly, weighing high-purity Si powder and ZrB according to a certain proportion2Powder and Yb2Si2O7Powder (Si: 45 wt.%, ZrB)2：30wt.％，Yb2Si2O7: 25 wt.%), mixing uniformly, adding 8 wt.% of PVA solution, the concentration of PVA solution is 6 wt.%, ball-milling with a ball mill to obtain uniform slurry, and spray-drying to obtain spherical powder. Adopting a plasma spraying process to spray at a spraying voltage of 385V, a spraying current of 115A and a main gas flow (Ar) of 4.8m3H, flow rate of auxiliary gas (He)1.0m3H, the spraying speed is 15g/min, the spraying distance is 80mm, and Si-Yb with the thickness of about 90 mu m is prepared on the surface of the SiC coating2Si2O7-ZrB2And (4) an anti-oxidation coating.
The coating thickness obtained in this example was 180 μm. SiC/Si-Yb2Si2O7-ZrB2The coating can effectively protect the C/C composite material for 410h in an air atmosphere at 1600 ℃, and the weight loss rate is 0.87%.
Example two
Taking out the sample with the density of 1.75g/cm3The thermostructural composite material of (1) is processed into a sample of 10mm multiplied by 10mm, is polished by SiC sand paper, and is ultrasonically cleaned in absolute ethyl alcohol for 25 min; and drying the cleaned thermostructural composite material sample at the temperature of 120 ℃ for 20 hours for later use.
Putting the cleaned sample of the thermal structure composite material into a quartz tube with through holes at two ends, heating a muffle furnace by a program temperature control device, setting the pre-oxidation temperature to 950 ℃, putting the quartz tube filled with the thermal structure composite material into the muffle furnace when the temperature of the muffle furnace is raised to 950 ℃ and is constant, putting the tube body part filled with the sample into the middle of the furnace chamber, namely a constant temperature area, ensuring that the pre-oxidation temperature of the sample is 950 ℃ and the pre-oxidation time is 6 min. And taking the quartz tube out of the muffle furnace chamber after the pre-oxidation time is reached, placing the quartz tube on a platform in a room temperature environment, naturally cooling the sample to room temperature, and weighing for later use.
Mixing Si powder, C powder and Al powder2O3Uniformly mixing the powder according to the mass ratio of 70%, 25% and 5%, putting the powder into a graphite crucible as embedding powder, putting the crucible into a high-temperature vacuum graphitization furnace, preserving the heat for 2 hours at 1800-2000 ℃ under the protection of argon gas, preparing a SiC coating on the surface of the thermostructural composite material, polishing the SiC coating by using sand paper to flatten the surface of the coating, and cleaning and drying the coating.
Preparation of Si-Yb by plasma spraying2Si2O7-ZrB2And (4) an anti-oxidation coating. Firstly, weighing high-purity Si powder and ZrB according to a certain proportion2Powder and Yb2Si2O7Powder (Si: 48 wt.%, ZrB)2：26wt.％，Yb2Si2O7: 26 wt.%), mixing uniformly, adding 15 wt.% PVA solution with concentration of 8 wt.%, and ball-milling with ball mill to obtainThe uniform slurry is spray dried to prepare spherical powder. Adopting a plasma spraying process to spray at 425V of spraying voltage, 140A of spraying current and 6.2m of main gas flow (Ar)3H, flow rate of auxiliary gas (He)1.5m3The spraying speed is 25g/min, the spraying distance is 100mm, and Si-Yb with the thickness of about 100 mu m is prepared on the surface of the SiC coating2Si2O7-ZrB2And (4) an anti-oxidation coating.
The coating thickness obtained in this example was 210 μm. SiC/Si-Yb2Si2O7-ZrB2The coating can effectively protect the C/C composite material for 465h in an air atmosphere at 1600 ℃, and the weight loss rate is 1.10%.
EXAMPLE III
Taking out the sample with the density of 1.75g/cm3The thermostructural composite material of (1) is processed into a sample of 10mm multiplied by 10mm, is polished by SiC sand paper, and is ultrasonically cleaned in absolute ethyl alcohol for 20 min; and drying the cleaned thermostructural composite material sample at the temperature of 120 ℃ for 18h for later use.
Putting the cleaned sample of the thermal structure composite material into a quartz tube with through holes at two ends, heating a muffle furnace by a program temperature control device, setting the pre-oxidation temperature to be 1000 ℃, putting the quartz tube filled with the thermal structure composite material into the muffle furnace when the temperature of the muffle furnace is raised to 1000 ℃ and is constant, and putting the tube body part filled with the sample into the middle of the furnace chamber, namely a constant temperature area, so as to ensure that the pre-oxidation temperature of the sample is 1000 ℃ and the pre-oxidation time is 5 min. And taking the quartz tube out of the muffle furnace chamber after the pre-oxidation time is reached, placing the quartz tube on a platform in a room temperature environment, naturally cooling the sample to room temperature, and weighing for later use.
Mixing Si powder, C powder and Al powder2O3Uniformly mixing 65%, 20% and 15% of powder by mass, putting the powder into a graphite crucible as embedding powder, putting the crucible into a high-temperature vacuum graphitization furnace, preserving the heat for 2 hours at 1800-2000 ℃ under the protection of argon gas, preparing a SiC coating on the surface of the thermostructural composite material, polishing the SiC coating by using sand paper to flatten the surface of the coating, and cleaning and drying the coating.
Preparation of Si-Yb by plasma spraying2Si2O7-ZrB2And (4) an anti-oxidation coating. Firstly, weighing high-purity Si powder and ZrB according to a certain proportion2Powder and Yb2Si2O7Powder (Si: 30 wt.%, ZrB)2：36wt.％，Yb2Si2O7: 34 wt.%), mixing uniformly, adding 12 wt.% PVA solution with concentration of 7 wt.%, ball-milling with ball mill to obtain uniform slurry, and spray-drying to obtain spherical powder. Adopting a plasma spraying process, wherein the spraying voltage is 400V, the spraying current is 127A, and the main gas flow (Ar) is 5.3m3H, flow rate of auxiliary gas (He)1.3m3H, the spraying speed is 20g/min, the spraying distance is 90mm, and Si-Yb with the thickness of about 110 mu m is prepared on the surface of the SiC coating2Si2O7-ZrB2And (4) an anti-oxidation coating.
The coating thickness obtained in this example was 220 μm. SiC/Si-Yb2Si2O7-ZrB2The coating can effectively protect the C/C composite material 473h at 1600 ℃ in air atmosphere, and the weight loss rate is 1.46%.
According to the preparation method of the high-temperature oxidation-resistant composite coating of the thermostructural composite material, after long-time high-temperature oxidation, the oxidation-resistant coating can be divided into three layers: unreacted layer of SiO2A glass layer and a Zr-Si-O glass layer. Zr-Si-O glass layer and SiO2The glass layer separates and covers it, has greater viscosity and lower oxygen permeability, and is more effective in providing antioxidant protection. Yb of2Si2O7The thermal expansion coefficient of the coating is small, the coating has extremely low oxygen permeability and water vapor permeability, and the environmental barrier performance of the coating is enhanced while the oxidation resistance of the thermostructural composite material is improved. The preparation method of the high-temperature antioxidant composite coating of the thermostructural composite material according to the embodiment of the invention has the advantages of simple preparation process, convenient operation, easily obtained raw materials and lower preparation cost.
In the description of the present invention, it is to be understood that "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (4)

1. The preparation method of the high-temperature anti-oxidation composite coating of the thermostructure composite material is characterized by comprising the following steps:
pre-oxidation: preserving the heat of the thermostructural composite material for 3-6 min at the temperature of 900-1000 ℃, and naturally cooling the thermostructural composite material to room temperature after preoxidation;
preparing a SiC coating: embedding the thermostructural composite material into the embedded powder under a protective atmosphere, and preserving heat for a second preset time at a second preset temperature to obtain the thermostructural composite material with the SiC coating;
preparation of Si-Yb2Si2O7-ZrB2Coating: spraying the spraying powder on the thermal structure composite material with the SiC coating by adopting a plasma spraying method under the voltage of 385-425V and the current of 115A-140A to prepare Si-Yb2Si2O7-ZrB2Coating; the spraying speed is 15 g/min-25 g/min, and the spraying distance is 80 mm-100 mm;
wherein the embedded powder at least comprises Si powder, C powder and Al powder2O3Pulverizing; in the embedded powder, the weight ratio of the Si powder is 65-80%, the weight ratio of the C powder is 10-25%, and the Al powder is2O3The weight ratio of the powder is 5-15%, the second preset temperature is 1800-2000 ℃, and the second preset time is 1-3 h; in the embedded powder, the grain diameter of the Si powder is 20-30 mu m, the grain diameter of the C powder is 20-30 mu m, and the Al powder2O3The particle size of the powder is 20-30 μm;
the spraying powder at least comprises Yb2Si2O7Powder ZrB2Powder, and Si powder; in the spray powder, Yb2Si2O7The weight ratio of the powder is 20-36 percent, and the ZrB2The weight ratio of the powder is 26-40%, and the weight ratio of the Si powder is 30-48%.
2. A method of making a thermostructural composite material high temperature oxidation resistant composite coating according to claim 1, further comprising, before the pre-oxidation step, the step of pre-treating: polishing the surface of the ultra-high temperature composite material, cleaning and drying, wherein the drying temperature is 110-130 ℃, and the drying time is 10-20 h.
3. A thermostructural composite high temperature oxidation resistant composite coating prepared according to the method of claim 1 or 2, comprising:
a thermostructural composite material;
a SiC coating covering the thermostructural composite;
Si-Yb2Si2O7-ZrB2coating of Si-Yb2Si2O7-ZrB2A coating covers the SiC coating.
4. The thermostructural composite high temperature oxidation resistant composite coating of claim 3, wherein the Si-Yb is2Si2O7-ZrB2The thickness of the coating is 90-110 μm.
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