CN114163260B - Ceramic matrix composite system on surface of unmanned aerial vehicle and preparation method thereof - Google Patents
Ceramic matrix composite system on surface of unmanned aerial vehicle and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
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- 229910052786 argon Inorganic materials 0.000 claims description 46
- 239000001257 hydrogen Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 46
- 238000007750 plasma spraying Methods 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 31
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- 229910010271 silicon carbide Inorganic materials 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
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- 238000005524 ceramic coating Methods 0.000 claims description 9
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- 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
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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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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Abstract
The invention discloses a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof, and the ceramic matrix composite system comprises a ceramic matrix composite substrate, wherein the ceramic matrix composite substrate is covered on the surface of an aircraft body, and a bonding layer, an oxygen barrier layer, an oxygen transmission barrier layer, a thermal expansion coefficient buffer layer and a heat insulation and cooling layer are sequentially deposited on the ceramic matrix composite substrate; the thickness of the bonding layer is 100-200 mu m, the thickness of the oxygen propagation resisting layer is 30-50 mu m, the thickness of the thermal expansion coefficient buffer layer is 30-50 mu m, and the thickness of the heat insulation and temperature reduction layer is 100-1000 mu m. The ceramic matrix composite system prepared by the invention has a remarkable high-temperature-resistant, high-heat-insulation, antioxidant and high-oxygen-resistant coating, so that the ceramic matrix composite system can be used for long-term service in high-temperature fire rescue, the service temperature exceeds 1000 ℃, the temperature of internal parts of the unmanned aerial vehicle for fire scene rescue is ensured to be below the limit working temperature, and meanwhile, the surface ceramic matrix composite ceramic material has extremely strong antioxidant performance.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof.
Background
With the deep research and application of the unmanned aerial vehicle, the maximum takeoff weight of the unmanned aerial vehicle reaches more than ten tons at present, the unmanned low-altitude aircraft is used for carrying out tasks such as fire extinguishing action, personnel rescue, communication connection, substance conveying and the like on a fire rescue site, the danger of a traditional pilot when the traditional pilot carries out the task can be effectively reduced, and meanwhile, the unmanned low-altitude aircraft has the advantages of small size, easiness in operation, small limitation on the takeoff site when carrying out fire rescue in a city, and is more suitable for the modern development trend. However, in order to effectively reduce the weight of the aircraft itself and at the same time increase the substances that it can carry. However, in the prior art, different resin-based composite materials or ceramic-based composite materials are generally used for manufacturing the fuselage of the low-altitude aircraft; the resin-based composite material has the problems of low melting point, insufficient high-temperature resistance and failure caused by easy smoke corrosion in a fire scene, so that the application of the resin-based composite material in large-scale fire and high-temperature fire scenes is limited; the ceramic matrix composite is silicon carbide fiber reinforced silicon carbide, carbon fiber reinforced carbon, carbon fiber reinforced silicon carbide, silicon carbide fiber reinforced carbon ceramic matrix composite and the like, the melting point of the ceramic matrix composite exceeds 2000 ℃, and the ceramic matrix composite has the advantages of low density, strong plasticity, high specific strength and the like similar to those of resin matrix composites, but the ceramic matrix composite has the defect that contact air at high temperature can be oxidized and failed, and a fire rescue unmanned aerial vehicle needs to be in service in a high-temperature environment for a long time, and simultaneously provides the effects of heat insulation and temperature reduction to ensure that internal parts of the unmanned aerial vehicle are below the limit working temperature. Therefore, the ability of providing oxidation resistance and oxygen transmission resistance for the ceramic matrix composite is the key for realizing the application of the ceramic matrix composite in the fire rescue unmanned aerial vehicle.
In view of the above, there is a need to develop a ceramic matrix composite system for unmanned aerial vehicle surface and a method for preparing the same to solve the above technical problems.
Disclosure of Invention
The invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof, which are used for solving the problems that the surface material of the body of the fire rescue unmanned aerial vehicle cannot resist high temperature and oxidation and the ceramic matrix composite is difficult to apply at high temperature; the invention enables the working temperature of the silicon carbide fiber reinforced silicon carbide, carbon fiber reinforced carbon, carbon fiber reinforced silicon carbide and silicon carbide fiber reinforced carbon ceramic matrix composite material matrix in the air to exceed 1000 ℃, and the related rescue unmanned aerial vehicle can be in service for a long time on a fire rescue site.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle, which comprises a ceramic matrix composite substrate, wherein the ceramic matrix composite substrate is covered on the surface of an aircraft body, and a bonding layer, an oxygen barrier layer, an oxygen propagation barrier layer, a thermal expansion coefficient buffer layer and a heat insulation and cooling layer are sequentially prepared on the ceramic matrix composite substrate; the thickness of the bonding layer is 100-200 mu m, the thickness of the oxygen propagation resisting layer is 30-50 mu m, the thickness of the thermal expansion coefficient buffer layer is 30-50 mu m, and the thickness of the heat insulation and temperature reduction layer is 100-1000 mu m.
Preferably, the thermal expansion coefficient of the oxygen propagation barrier layer is 3-6 × 10 -6 K -1 The buffer layer has a thermal expansion coefficient of 6-9 × 10 -6 K -1 The thermal expansion coefficient of the heat insulation and temperature reduction layer is 9-11 multiplied by 10 -6 K -1 。
Preferably, the ceramic matrix composite substrate is one of silicon carbide fiber reinforced silicon carbide, carbon fiber reinforced carbon, carbon fiber reinforced silicon carbide and silicon carbide fiber reinforced carbon.
Preferably, the bonding layer is formed by spraying a Ta material on the surface of the ceramic matrix composite substrate by a cold spraying method.
By adopting the method, the metal tantalum with excellent chemical compatibility with the ceramic matrix composite is selected as the bonding layer, so that the reaction between the matrix material and the bonding layer can be effectively inhibited, and the long-term effective service of the coating is ensured; the compact tantalum coating can be prepared by cold spraying or electron beam physical vapor deposition, the interior of the coating is ensured not to be oxidized, and the surface of the metal tantalum is in contact with air and oxidized after the metal tantalum is placed in the air for a period of time to form a compact oxygen barrier Ta 2 O 5 And the process is simplified.
Preferably, the oxygen barrier layer is Ta 2 O 5 。
Preferably, the oxygen propagation resisting layer is rare earth tantalate (RETaO) 4 A ceramic coating; wherein RE is composed of one or more rare earth elements.
Preferably, the thermal expansion coefficient buffer layer is RETa 3 O 9 A ceramic, wherein RE consists of one or more of the rare earth elements.
Preferably, the heat insulation and temperature reduction layer is RE 3 TaO 7 Ceramic, wherein RE consists of one or more of the rare earth elements.
By adopting the method, the oxygen propagation resisting layer, the thermal expansion coefficient buffer layer and the heat insulation and temperature reduction layer are respectively rare earth tantalate RETaO 4 、RETa 3 O 9 And RE 3 TaO 7 They all have sufficient tantalum element, ensure that the components do not react with each other, and have excellent chemical compatibility with the oxygen barrier layer and the bonding layer; oxygen-propagation-blocking layer RETaO 4 The ceramic has defect-free crystal lattice and extremely weak oxygen ion propagation performance, so that the propagation of oxygen into the interior to react with the ceramic matrix can be effectively prevented, and the RETaO 4 The ceramic has a thermal expansion coefficient (3-6 x 10) similar to that of the ceramic matrix composite -6 K -1 ) The thermal stress generated by the thermal expansion coefficient difference is effectively reduced, and the service life of the coating is prolonged; preparing a thermal expansion coefficient buffer layer RETa between the heat insulation and temperature reduction layer and the oxygen transmission resisting layer 3 O 9 The ceramic effectively reduces the difference of the thermal expansion coefficients between the two layers, effectively reduces the thermal stress generated by the difference of the thermal expansion coefficients, and prolongs the service life of the coating; rare earth tantalate (RETaO) 4 、RETa 3 O 9 And RE 3 TaO 7 All have extremely low thermal conductivity, thereby providing excellent heat insulation and cooling effects; meanwhile, the multilayer structure combined with the whole material system provides interface thermal resistance, so that the internal temperature of the unmanned aerial vehicle is further reduced, internal parts of the unmanned aerial vehicle can be guaranteed to be in service at the limit working temperature, and finally the fire rescue unmanned aerial vehicle can be used in a high-temperature environment for a long time.
The second purpose of the invention is to provide a preparation method of the ceramic matrix composite system on the surface of the unmanned aerial vehicle, which comprises the following steps:
s1, preparing a bonding layer with the thickness of 100-200 mu m on the upper surface of a ceramic matrix composite substrate by using a cold spraying method;
s2: placing the bonding layer in the S1 in the air for oxidation to obtain an oxygen barrier layer with the thickness less than 1 mu m;
s3: preparing an oxygen-barrier propagation layer with the thickness of 30-50 mu m on the surface of the oxygen-barrier layer in the S2 by utilizing an atmospheric plasma spraying method;
s4: preparing a thermal expansion coefficient buffer layer with the thickness of 30-50 micrometers on the surface of the oxygen propagation resisting layer in the step S3 by utilizing an atmospheric plasma spraying method;
s5: and preparing a heat-insulating and temperature-reducing ceramic layer with the thickness of 100-1000 microns on the surface of the thermal expansion coefficient buffer layer in the step S4 by using an atmospheric plasma spraying method.
Preferably, in the cold spraying process in the step S1, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding rate is 40g/min; in the process of spraying the oxygen barrier propagation layer by using the atmospheric plasma spraying method in the S3, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the flow rates of argon and hydrogen are 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/S, and the spraying time is 1min; in the process of spraying the thermal expansion coefficient buffer layer by using the atmospheric plasma spraying method in the S4, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the flow rates of the argon and the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/S, and the spraying time is 2min; in the S5, the argon is used as protective gas, the hydrogen is used as combustion gas, the power of the spray gun is 46kW, the distance between the spray gun is 150mm, the gas flow of the argon and the hydrogen is 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/S, and the spraying time is 2min.
In summary, compared with the prior art, the invention has the advantages that:
according to the technical scheme, the bonding layer, the oxidation resistant layer, the oxygen barrier layer, the thermal expansion coefficient buffer layer and the heat insulation and temperature reduction layer are sequentially prepared on the surface of the ceramic matrix composite material, so that the effects of heat insulation and temperature reduction, oxygen transmission resistance and oxidation resistance can be provided for the ceramic matrix composite material; meanwhile, the thermal expansion coefficient buffer layer can effectively reduce the thermal expansion coefficient difference between the heat insulation and cooling layer and the oxygen transmission resisting layer, thereby reducing the thermal stress and prolonging the service life of the coating system; when the material system is used as a fire rescue unmanned aerial vehicle body material, the advantage that the heat insulation and cooling effects are improved by using the low heat conductivity and the multilayer structure can ensure that the internal parts of the body are under the limit service temperature of the internal parts under the service environment of a fire scene, so that the internal parts can be effectively used for a long time.
Drawings
FIG. 1 is a schematic view of a surface ceramic matrix composite system of an unmanned aerial vehicle according to the present invention;
FIG. 2 is a graph showing the comparison of the thermal conductivity of the ceramic matrix composite system and the surface heat insulating and temperature reducing layer prepared according to the present invention;
FIG. 3 is a drawing of a top coating of a ceramic matrix composite system made in accordance with the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
Example 1:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to FIG. 1, according to an embodiment of the present invention, a silicon carbide fiber reinforced ceramic matrix is includedA bonding layer with the thickness of 100 mu m, an oxygen barrier layer with the thickness less than 1 mu m, an oxygen transmission barrier layer with the thickness of 30 mu m, a thermal expansion coefficient buffer layer with the thickness of 30 mu m and a heat insulation and temperature reduction layer with the thickness of 100m are deposited in sequence; adopting metal tantalum Ta as a material of a bonding layer; the oxygen transmission resisting layer adopts rare earth tantalate RETaO 4 A ceramic coating, wherein RE is Yb; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is Tm.
The method comprises the following specific steps: (1) Preparing a tantalum Ta bonding layer with the thickness of 100 mu m on the upper surface of the silicon carbide fiber reinforced silicon carbide substrate by using a cold spraying method; in the cold spraying process, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding speed is 40g/min; after the material sprayed with the tantalum Ta bonding layer is placed in the air, the metal tantalum is oxidized to form compact tantalum oxide Ta with the thickness of less than 1 mu m on the surface of the metal tantalum 2 O 5 An oxygen barrier layer.
(2) Compacting tantalum oxide Ta 2 O 5 Preparing an oxygen transmission resisting layer YbTaO with the thickness of 30 microns on the surface of the oxygen resisting layer by an atmospheric plasma spraying method 4 And (3) coating the ceramic. First using Yb 2 O 3 And Ta 2 O 5 Preparing spherical YbTaO by high-temperature solid-phase method 4 Spherical powder; in the process of spraying the oxygen barrier propagation layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the flow rates of the argon and the hydrogen are 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 1min.
(3) By atmospheric plasma spraying, in YbTaO 4 Preparing 30-micrometer-thick thermal expansion coefficient buffer layer TmTA on the surface of the ceramic oxygen-barrier propagation layer 3 O 9 And (3) coating the ceramic. First using Tm 2 O 3 And Ta 2 O 5 Preparing spherical TmTa from the raw material by a high-temperature solid-phase method 3 O 9 Spherical powder; in the process of spraying the thermal expansion coefficient buffer layer by using an atmospheric plasma spraying method, argon is used as protective gas, and hydrogen is used as hydrogenAnd (3) combustion gas, wherein the power of the spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow rates of argon and hydrogen are 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(4) By atmospheric plasma spraying at TmTa 3 O 9 Preparing a heat-insulating and temperature-reducing ceramic layer Tm with the thickness of 200 microns on the surface of the ceramic thermal expansion coefficient buffer layer 3 TaO 7 And (3) coating the ceramic. First using Tm 2 O 3 And Ta 2 O 5 Preparing spherical Tm from raw materials by a high-temperature solid-phase method 3 TaO 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow of the argon and the gas flow of the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
Example 2:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to FIG. 1, according to an embodiment of the present invention, a SiC-based carbon ceramic matrix is provided, on which a 200 μm thick bonding layer, an oxygen barrier layer less than 1 μm thick, an oxygen propagation barrier layer 50 μm thick, a 50 μm thick buffer layer with a thermal expansion coefficient, and a 100m thick insulating and cooling layer are sequentially deposited; adopting metal tantalum Ta as a material of a bonding layer; the oxygen transmission resisting layer adopts rare earth tantalate RETaO 4 The ceramic coating, wherein RE is Yb and Lu; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is La, ho and Tm.
The method comprises the following specific steps: (1) Preparing a tantalum Ta bonding layer with the thickness of 200 mu m on the upper surface of the silicon carbide fiber reinforced silicon carbide substrate by using a cold spraying method; in the cold spraying process, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding speed is 40g/min; after the material sprayed with the tantalum Ta bonding layer is placed in the air, the metal tantalum is oxidized to form a thick layer on the surface of the metal tantalumDense tantalum oxide Ta with a degree of less than 1 μm 2 O 5 An oxygen barrier layer.
(2) Compacting tantalum oxide Ta 2 O 5 Preparing oxygen-barrier propagation layer Yb with thickness of 50 microns on the surface of the oxygen-barrier layer by using an atmospheric plasma spraying method 1/2 Lu 1/2 TaO 4 And (3) coating the ceramic. First use Lu 2 O 3 、Yb 2 O 3 And Ta 2 O 5 Preparing spherical Yb from the raw material by a high-temperature solid-phase method 1/2 Lu 1/2 TaO 4 Spherical powder; in the process of spraying the oxygen-blocking propagation layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the gas flow of the argon and the hydrogen is 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(3) By atmospheric plasma spraying on Yb 1/2 Lu 1/2 TaO 4 Preparing a 50-micrometer-thick thermal expansion coefficient buffer layer La on the surface of the ceramic oxygen-barrier propagation layer 1/3 Ho 1/3 Tm 1/3 Ta 3 O 9 And (3) coating the ceramic. First use La 2 O 3 、Ho 2 O 3 、Tm 2 O 3 And Ta 2 O 5 Preparing spherical La by using high-temperature solid-phase method as raw material 1/3 Ho 1/3 Tm 1/3 Ta 3 O 9 Spherical powder; in the process of spraying the thermal expansion coefficient buffer layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the flow rates of the argon and the hydrogen are 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 3min.
(4) By atmospheric plasma spraying, in La 1/3 Ho 1/3 Tm 1/3 Ta 3 O 9 Preparing a heat-insulating and temperature-reducing ceramic layer Y with the thickness of 100 microns on the surface of the ceramic thermal expansion coefficient buffer layer 3 TaO 7 And (3) coating the ceramic. First using Y 2 O 3 And Ta 2 O 5 Preparing spherical Y from raw materials by a high-temperature solid-phase method 3 TaO 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow of the argon and the gas flow of the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
Example 3:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to fig. 1, according to an embodiment of the present invention, a carbon fiber reinforced silicon carbide ceramic matrix is included, on which an adhesion layer with a thickness of 150 μm, an oxygen barrier layer with a thickness less than 1 μm, an oxygen propagation barrier layer with a thickness of 35 μm, a thermal expansion coefficient buffer layer with a thickness of 35 μm, and a thermal insulation and cooling layer with a thickness of 1000 μm are sequentially deposited; adopting metal tantalum Ta as a material of a bonding layer; the oxygen barrier layer adopts rare earth tantalate RETaO 4 A ceramic coating, wherein RE is Sc; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is La.
The method specifically comprises the following steps: (1) Preparing a tantalum Ta bonding layer with the thickness of 150 mu m on the upper surface of the silicon carbide fiber reinforced silicon carbide substrate by using a cold spraying method; in the cold spraying process, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding speed is 40g/min; after the material sprayed with the tantalum Ta bonding layer is placed in the air, the metal tantalum is oxidized to form compact tantalum oxide Ta with the thickness of less than 1 mu m on the surface of the metal tantalum 2 O 5 An oxygen barrier layer.
(2) Compacting tantalum oxide Ta 2 O 5 Preparing an oxygen transmission resisting layer ScTaO with the thickness of 35 microns on the surface of the oxygen resistance layer by an atmospheric plasma spraying method 4 And (3) coating the ceramic. First using Sc 2 O 3 And Ta 2 O 5 Preparing spherical ScTaO serving as a raw material by a high-temperature solid-phase method 4 Spherical powder; spraying oxygen-barrier layer by atmospheric plasma sprayingIn the process, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the gas flow rates of the argon and the hydrogen are 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(3) By atmospheric plasma spraying on ScTaO 4 Preparing 35-micron-thick thermal expansion coefficient buffer layer LaTa on surface of ceramic oxygen-barrier propagation layer 3 O 9 And (3) coating the ceramic. First use La 2 O 3 And Ta 2 O 5 Preparing spherical LaTa from the raw material by a high-temperature solid-phase method 3 O 9 Spherical powder; in the process of spraying the thermal expansion coefficient buffer layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow rates of the argon and the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 3min.
(4) By atmospheric plasma spraying on LaTa 3 O 9 Preparing a heat-insulating and temperature-reducing ceramic layer YLaDyTaO with the thickness of 1000 microns on the surface of the ceramic thermal expansion coefficient buffer layer 7 And (3) coating the ceramic. First using Y 2 O 3 、La 2 O 3 、Dy 2 O 3 And Ta 2 O 5 Preparing spherical YLaDyTaO by high-temperature solid-phase method 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the flow rates of the argon and the hydrogen are 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 10min.
Example 4:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to FIG. 1, in accordance with an embodiment of the present invention, a carbon fiber reinforced carbon substrate is included, and a carbon fiber reinforced carbon substrate is sequentially deposited thereonThe adhesive layer with the thickness of 170 mu m, the oxygen barrier layer with the thickness less than 1 mu m, the oxygen propagation barrier layer with the thickness of 35 mu m, the thermal expansion coefficient buffer layer with the thickness of 40 mu m and the heat insulation and temperature reduction layer with the thickness of 500 m; adopting metal tantalum Ta as a material of a bonding layer; the oxygen barrier layer adopts rare earth tantalate RETaO 4 The ceramic coating, wherein RE is Sc, yb and Lu; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is La, ho, er and Tm.
The method specifically comprises the following steps: (1) Preparing a tantalum Ta bonding layer with the thickness of 170 mu m on the upper surface of the silicon carbide fiber reinforced silicon carbide substrate by using a cold spraying method; in the cold spraying process, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding speed is 40g/min; after the material sprayed with the tantalum Ta bonding layer is placed in the air, the metal tantalum is oxidized to form compact tantalum oxide Ta with the thickness of less than 1 mu m on the surface of the metal tantalum 2 O 5 An oxygen barrier layer.
(2) Compacting tantalum oxide Ta 2 O 5 Preparing an oxygen transmission barrier layer Sc with the thickness of 35 microns on the surface of the oxygen barrier layer by an atmospheric plasma spraying method 1/3 Yb 1/3 Lu 1/3 TaO 4 And (3) coating the ceramic. First using Sc 2 O 3 、Lu 2 O 3 、Yb 2 O 3 And Ta 2 O 5 Preparing spherical Sc serving as a raw material by a high-temperature solid-phase method 1/3 Yb 1/3 Lu 1/3 TaO 4 Spherical powder; in the process of spraying the oxygen-blocking propagation layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the gas flow of the argon and the hydrogen is 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(3) By atmospheric plasma spraying, in Sc 1/3 Yb 1/3 Lu 1/3 TaO 4 Preparing a thermal expansion coefficient buffer layer La with the thickness of 40 microns on the surface of the oxygen barrier propagation layer of the ceramic 1/4 Ho 1/4 Tm 1/4 Er 1/4 Ta 3 O 9 And (3) coating the ceramic. First, er was used 2 O 3 、La 2 O 3 、Ho 2 O 3 、Tm 2 O 3 And Ta 2 O 5 Preparing spherical La by using high-temperature solid-phase method as raw material 1/4 Ho 1/4 Tm 1/4 Er 1/4 Ta 3 O 9 Spherical powder; in the process of spraying the thermal expansion coefficient buffer layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow rates of the argon and the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 3min.
(4) By atmospheric plasma spraying, in La 1/4 Ho 1/4 Tm 1/4 Er 1/4 Ta 3 O 9 Preparing a heat-insulating and temperature-reducing ceramic layer Y with the thickness of 500 microns on the surface of the ceramic thermal expansion coefficient buffer layer 3 TaO 7 And (3) coating the ceramic. First using Y 2 O 3 And Ta 2 O 5 Preparing spherical Y from raw materials by a high-temperature solid-phase method 3 TaO 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the flow rates of the argon and the hydrogen are 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 10min.
Comparative example 1:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to FIG. 1, according to an embodiment of the present invention, a ceramic matrix composite material matrix silicon carbide fiber reinforced carbon is included, on which a bonding layer with a thickness of 200 μm, an oxygen barrier layer with a thickness of less than 1 μm, an oxygen propagation barrier layer with a thickness of 50 μm, and an insulating and cooling layer with a thickness of 100m are sequentially deposited; adopting metal tantalum Ta as a material of a bonding layer; the oxygen barrier layer adopts rare earth tantalate RETaO 4 The ceramic coating, wherein RE is Yb and Lu; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is La, ho and Tm.
The method comprises the following specific steps: (1) Preparing a tantalum Ta bonding layer with the thickness of 200 mu m on the upper surface of the silicon carbide fiber reinforced silicon carbide substrate by using a cold spraying method; in the cold spraying process, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding speed is 40g/min; after the material sprayed with the tantalum Ta bonding layer is placed in the air, the metal tantalum is oxidized to form compact tantalum oxide Ta with the thickness of less than 1 mu m on the surface of the metal tantalum 2 O 5 An oxygen barrier layer.
(2) Compacting tantalum oxide Ta 2 O 5 Preparing oxygen-barrier propagation layer Yb with thickness of 50 microns on the surface of the oxygen-barrier layer by using an atmospheric plasma spraying method 1/2 Lu 1/2 TaO 4 And (3) coating the ceramic. First use Lu 2 O 3 、Yb 2 O 3 And Ta 2 O 5 Preparing spherical Yb from the raw material by a high-temperature solid-phase method 1/2 Lu 1/2 TaO 4 Spherical powder; in the process of spraying the oxygen-blocking propagation layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the gas flow of the argon and the hydrogen is 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(3) By atmospheric plasma spraying method, in the oxygen diffusion barrier layer Yb 1/2 Lu 1/2 TaO 4 Preparing a heat-insulating and temperature-reducing ceramic layer Y with the thickness of 100 microns on the surface of the ceramic coating 3 TaO 7 And (3) coating the ceramic. First using Y 2 O 3 And Ta 2 O 5 Preparing spherical Y from raw materials by a high-temperature solid-phase method 3 TaO 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow of the argon and the gas flow of the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
Comparative example 2:
the invention provides a ceramic matrix composite system on the surface of an unmanned aerial vehicle and a preparation method thereof. Referring to FIG. 1, according to an embodiment of the present invention, the carbon fiber reinforced silicon carbide ceramic matrix is provided, on which an oxygen propagation barrier layer with a thickness of 35 μm, a thermal expansion coefficient buffer layer with a thickness of 35 μm, and a thermal insulation and cooling layer with a thickness of 1000 μm are sequentially deposited; adopting metal tantalum Ta as a material of a bonding layer; the oxygen barrier layer adopts rare earth tantalate RETaO 4 A ceramic coating, wherein RE is Sc; the thermal expansion coefficient buffer layer adopts RETa 3 O 9 Ceramic, wherein RE is La.
The method comprises the following specific steps: (1) Preparing an oxygen transmission resisting layer ScTaO with the thickness of 35 microns on the surface of a matrix by an atmospheric plasma spraying method 4 And (3) coating the ceramic. First using Sc 2 O 3 And Ta 2 O 5 Preparing spherical ScTaO serving as raw material by a high-temperature solid-phase method 4 Spherical powder; in the process of spraying the oxygen barrier propagation layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the flow rates of the argon and the hydrogen are 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/s, and the spraying time is 2min.
(2) By atmospheric plasma spraying on ScTaO 4 Preparing 35-micron-thick thermal expansion coefficient buffer layer LaTa on surface of ceramic oxygen-barrier propagation layer 3 O 9 And (3) coating the ceramic. First, la was used 2 O 3 And Ta 2 O 5 Preparing spherical LaTa from the raw material by a high-temperature solid-phase method 3 O 9 Spherical powder; in the process of spraying the thermal expansion coefficient buffer layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow rates of the argon and the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 3min.
(3) By atmospheric plasmaSpraying method on LaTa 3 O 9 Preparing a heat-insulating and temperature-reducing ceramic layer YLaDyTaO with the thickness of 1000 microns on the surface of the ceramic thermal expansion coefficient buffer layer 7 And (3) coating the ceramic. First using Y 2 O 3 、La 2 O 3 、Dy 2 O 3 And Ta 2 O 5 Preparing spherical YLaDyTaO by high-temperature solid-phase method 7 Spherical powder; in the process of spraying the heat-insulating and cooling ceramic layer by using an atmospheric plasma spraying method, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the flow rates of the argon and the hydrogen are 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/s, and the spraying time is 10min.
The specific composition of the material system prepared in the above examples is shown in table 1. To characterize the performance of the examples and comparative examples, we tested the number of thermal cycles, oxidative weight loss, and adiabatic cooling gradients required for their failure. Wherein the thermal cycle test process comprises the steps of heating the surface of the coating to 1000 ℃ by using flame, preserving heat for 3 minutes, and then cooling for 2 minutes, and circulating the process until the coating is peeled off or the oxidation weight loss of the material exceeds 10%; after the mass of the material systems before (W1) and after (W2) the total thermal cycle times is weighed, (W1-W2)/W1 multiplied by 100 percent is the oxidation weight loss rate; and the temperature difference between the surface temperature of the coating and the contact interface of the substrate and the coating in the first test is the thermal insulation and cooling gradient of the coating material, and the result is shown in table 2.
TABLE 1
TABLE 2
| Number of thermal cycles | Oxidation weight loss ratio (%) | Heat insulation gradient (. Degree. C.) | |
| Example 1 | 303 | 12 | 482 |
| Example 2 | 317 | 15 | 409 |
| Example 3 | 1352 | 10 | 627 |
| Example 4 | 1068 | 13 | 516 |
| Comparative example 1 | 23 | 26 | 388 |
| Comparative example 2 | 16 | 22 | 611 |
Test results show that the material for preparing the complete coating system has excellent heat insulation and cooling effects, and can be used for a long time in service at the temperature of 1000 ℃, so that the oxidation failure of the matrix material is prevented; the material which is not prepared into a complete coating system fails early due to large difference of thermal expansion coefficients and weak binding force, so that the service requirement cannot be met.
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 do not necessarily 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.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that those skilled in the art may make variations, modifications, substitutions and alterations within the scope of the present invention without departing from the spirit and scope of the present invention.
Claims (4)
1. The utility model provides a ceramic matrix composite on unmanned aerial vehicle surface, includes ceramic matrix composite base member, its characterized in that: the ceramic matrix composite material substrate is covered on the surface of an aircraft fuselage, and a bonding layer, an oxygen barrier propagation layer, a thermal expansion coefficient buffer layer and a heat insulation and cooling layer are sequentially prepared on the ceramic matrix composite material substrate; the thickness of the bonding layer is 100-200 mu m, the thickness of the oxygen transmission resisting layer is 30-50 mu m, the thickness of the thermal expansion coefficient buffer layer is 30-50 mu m, and the thickness of the heat insulation and temperature reduction layer is 100-1000 mu m;
the ceramic matrix composite material matrix is silicon carbide fiber reinforced silicon carbide, carbon fiber reinforced carbon, carbon fiber reinforced silicon carbide and silicon carbide fiberOne of the vitamin enhancing carbons; the bonding layer is formed by spraying a Ta material on the surface of the ceramic matrix composite substrate by a cold spraying method; the oxygen barrier layer is Ta 2 O 5 (ii) a The oxygen transmission resisting layer is rare earth tantalate (RETaO) 4 A ceramic coating; the thermal expansion coefficient buffer layer is RETa 3 O 9 A ceramic; the heat insulation and temperature reduction layer is RE 3 TaO 7 A ceramic;
wherein RE is one or more of rare earth elements, and RE in different layers can be the same or different.
2. The ceramic matrix composite of a drone surface of claim 1, wherein the oxygen propagation barrier layer has a coefficient of thermal expansion of 3-6 x 10 -6 K -1 The buffer layer has a thermal expansion coefficient of 6-9 × 10 -6 K -1 The thermal expansion coefficient of the heat insulation and temperature reduction layer is 9-11 multiplied by 10 -6 K -1 。
3. The method for preparing the ceramic matrix composite material on the surface of the unmanned aerial vehicle according to any one of claims 1 to 2, characterized by comprising the following steps:
s1, preparing a bonding layer with the thickness of 100-200 mu m on the upper surface of a ceramic matrix composite substrate by using a cold spraying method;
s2: placing the bonding layer in the S1 in the air for oxidation to obtain an oxygen barrier layer with the thickness less than 1 mu m;
s3: preparing an oxygen barrier propagation layer with the thickness of 30-50 mu m on the surface of the oxygen barrier layer in the step S2 by using an atmospheric plasma spraying method;
s4: preparing a thermal expansion coefficient buffer layer with the thickness of 30-50 microns on the surface of the oxygen barrier propagation layer in the step S3 by using an atmospheric plasma spraying method;
s5: and preparing a heat-insulating and temperature-reducing ceramic layer with the thickness of 100-1000 microns on the surface of the thermal expansion coefficient buffer layer in the step S4 by using an atmospheric plasma spraying method.
4. The method for preparing the ceramic matrix composite material on the surface of the unmanned aerial vehicle according to the claim 3, wherein in the cold spraying process in the step S1, compressed nitrogen is used as working gas, the spraying pressure is 0.66MPa, the spraying distance is 30mm, the spraying temperature is 800 ℃, and the powder feeding rate is 40g/min; in the process of spraying the oxygen barrier propagation layer by using the atmospheric plasma spraying method in the S3, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 42kW during spraying, the distance of the spray gun is 100mm, the flow rates of argon and hydrogen are 40/12slpm and 45/10slpm respectively, the feeding speed is 50g/min, the speed of the spray gun is 300mm/S, and the spraying time is 1min; in the process of spraying the thermal expansion coefficient buffer layer by using the atmospheric plasma spraying method in the S4, argon is used as protective gas, hydrogen is used as combustion gas, wherein the power of a spray gun is 46kW, the distance of the spray gun is 150mm, the gas flow rates of the argon and the hydrogen are respectively 42/12slpm and 40/10slpm, the feeding speed is 30g/min, the speed of the spray gun is 300mm/S, and the spraying time is 2min; in the S5, the argon is used as protective gas, the hydrogen is used as combustion gas, the power of the spray gun is 46kW, the distance between the spray gun is 150mm, the gas flow of the argon and the hydrogen is 42/12slpm and 40/10slpm respectively, the feeding speed is 30g/min, the speed of the spray gun is 300mm/S, and the spraying time is 2min.
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