A method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating

Abstract

This invention relates to a method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating, belonging to the technical field of wear-resistant and corrosion-resistant coating material preparation. The invention includes (1) preparing ZrAl powder-coated Al2O3 reinforcing particles; (2) preparing ZrAlCu powder-coated Al2O3 reinforcing particles; (3) preparing a particle-reinforced zirconium-based amorphous gradient composite coating material; and (4) spraying the particle-reinforced zirconium-based amorphous gradient composite coating material onto the substrate surface to form a coating. By using Al2O3 reinforcing particles, this invention overcomes the problems of high room-temperature brittleness and poor wear resistance in amorphous alloys. The preparation method yields a coating material with high hardness, good bonding strength, and excellent corrosion and wear resistance, providing more comprehensive protection to the substrate after coating formation.

Description

Technical Field

[0001] This invention belongs to the field of wear-resistant and corrosion-resistant coating material preparation technology, and relates to a method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating. Background Technology

[0002] Amorphous alloys have a disordered structure at the atomic scale, lacking defects such as dislocations and grain boundaries that are widely present in traditional metal alloys. This special structure gives them a series of excellent properties, such as high hardness and good corrosion resistance. Amorphous alloys are considered to be a new generation of high-performance engineering structural materials. However, because amorphous alloys lack grain boundaries and dislocations found in traditional crystalline materials, shear bands can expand rapidly and unimpeded once formed in amorphous alloys, making the material prone to failure along the shear bands. This results in high room temperature brittleness and poor wear resistance in amorphous alloys, which limits their use as coating materials.

[0003] Therefore, it is necessary to provide a method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating to obtain a particle-reinforced zirconium-based amorphous gradient composite coating material, so as to make up for the problems of high room temperature brittleness and poor wear resistance of amorphous alloys. Summary of the Invention

[0004] To overcome the problems in the prior art, this invention proposes a method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating. The method yields a coating material with high hardness, bonding strength, corrosion resistance, and wear resistance. After being sprayed onto the substrate, it provides more comprehensive protection for the substrate.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] The preparation method includes the following steps:

[0007] (1) First, Al2O3 reinforcing particles and paraffin particles are placed in a container, and the container is heated in a water bath while stirring to slowly melt the paraffin particles and allow them to adhere to the surface of the Al2O3 reinforcing particles. The Al2O3 reinforcing particles with paraffin adhering to their surface are then placed in a ball mill jar along with Zr powder and Al powder. Anhydrous ethanol is poured into the ball mill jar until the mixed powder is submerged. The mixture is then ball-milled under an argon atmosphere and dried to obtain Al2O3 reinforcing particles coated with ZrAl powder. Ball milling under an argon atmosphere prevents the Al2O3 particles from being oxidized during the milling process.

[0008] (2) Place the Al2O3 reinforcing particles coated with ZrAl powder in step (1) and the paraffin particles in a container, place the container in water for water bath heating, and stir to slowly melt the paraffin particles and attach them to the surface of the ZrAl powder coating layer. Place the Al2O3 reinforcing particles coated with ZrAl powder and the ZrAlCu amorphous powder into a ball mill jar, pour in anhydrous ethanol until the mixed powder is submerged, and then perform cyclic ball milling in an argon atmosphere. Then perform drying treatment to obtain Al2O3 reinforcing particles coated with ZrAlCu powder.

[0009] (3) The Al2O3 reinforcing particles coated with ZrAlCu powder obtained in step (2) are mixed with ZrAlCuNi amorphous powder and organic binder in a ball mill, and then dried to obtain an Al2O3 particle-reinforced zirconium-based amorphous gradient composite coating material with a gradient structure.

[0010] (4) The substrate is ground, sandblasted and ultrasonically cleaned, and then cleaned and dried with alcohol. Then, the particle-reinforced zirconium-based amorphous gradient composite coating material obtained in step (3) is sprayed onto the substrate surface to form a coating using supersonic flame spraying technology.

[0011] Preferably, in step (1), the particle size of Al2O3 reinforcing particles is 40-90 μm, the particle size of Zr powder and Al powder is 10-60 μm, the molar ratio of Zr powder to Al powder is Zr powder: Al powder = 1:1, and the mass ratio of Al2O3 reinforcing particles with paraffin attached to the surface to Zr powder and Al powder is 1:1.

[0012] Preferably, in step (2), the mass ratio of the Al2O3 reinforcing particles coated with ZrAl powder to the ZrAlCu amorphous powder is 1:1, the particle size of the ZrAlCu amorphous powder is 10-50 μm, and the atomic percentage of the ZrAlCu amorphous powder is: 45-60% Zr, 20-30% Al, and 15-25% Cu.

[0013] Preferably, in steps (1) and (2), the mass of paraffin particles added is 1-4% of the total mass of Al2O3 reinforcing particles and paraffin particles, the water bath heating temperature is 60-70℃, and the ball milling conditions are as follows: the mass ratio of the material to be milled to the grinding balls is 1:3, the planetary ball mill is used to mix the powder at a speed of 300-400 r / min, the ball milling time is 8-9 h, the drying temperature is 100-200℃, and the drying time is 1 h.

[0014] Preferably, in step (3), the atomic percentage of the ZrAlCuNi amorphous powder is: 45-60% Zr, 10-15% Al, 20-30% Cu, 5-10% Ni, the particle size of the ZrAlCuNi amorphous powder is 10-60 μm, the mass ratio of the ZrAlCu powder-coated Al2O3 reinforcing particles to the ZrAlCuNi amorphous powder is 1-2:1-3; the mass ratio of the ZrAlCu powder-coated Al2O3 reinforcing particles, the ZrAlCuNi amorphous powder, and the organic binder is 100:1, the ball milling speed is 400-600 r / min, the ball milling time is 5-8 h, and the powder is dried in a vacuum drying oven at 100 °C for 2 h.

[0015] Preferably, the organic adhesive is a water-soluble adhesive composed of paraffin wax, microcrystalline wax, and methyl ethyl ketone, wherein the mass ratio of paraffin wax: microcrystalline wax: methyl ethyl ketone is 6-7:1-2:0.5-1.

[0016] Preferably, in step (4), during the supersonic flame spraying process, the oxygen flow rate is 40-50 m³ / h. 3 / h, kerosene flow rate is 20~25L / h, powder feeding rate is 20~25g / min, spraying distance is 300~400mm, and spraying speed is 250~350mm / s.

[0017] Preferably, the coating thickness formed by spraying the particle-reinforced zirconium-based amorphous gradient composite material onto the substrate is 300–450 μm.

[0018] Al2O3 ceramic particles are uniformly embedded in a zirconium-based amorphous gradient composite coating and are coated by the coating. Compared with direct mixing, the interface between the Al2O3 particles and the amorphous matrix can interact. This interfacial interaction helps to hinder crack propagation and strengthen the fracture strength and improve the wear resistance of the zirconium-based amorphous gradient composite coating. The high hardness and stability of the Al2O3 ceramic particles, as well as their effective load transfer and energy absorption with the amorphous matrix, mean that the introduction of Al2O3 ceramic particles not only improves the mechanical properties of the zirconium-based amorphous gradient composite coating but also enhances its wear resistance through physical barriers and chemical stability.

[0019] The beneficial effects of this invention are:

[0020] 1. This invention uses Al2O3 ceramic particles to reinforce the amorphous coating, thereby improving the fracture strength of the amorphous alloy, compensating for the poor wear resistance of the amorphous alloy, and making the coating provide more comprehensive protection for the substrate.

[0021] 2. The present invention utilizes a gradient composite structure of coating materials to create a transition from crystalline to amorphous layers, allowing the crystalline layer to better combine with the amorphous layer and resulting in a stronger bond between the coating material and the substrate.

[0022] 3. The present invention uses supersonic flame spraying to spray a coating onto the substrate, which can effectively avoid the crystallization of amorphous alloys during the spraying process, prevent the coating material itself from being damaged, and obtain a clean, dense, fine and uniform coating. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the particle-reinforced zirconium-based amorphous coating and the substrate of the present invention.

[0024] Figure 2 The image shows the tribological wear test curves of the particle-reinforced zirconium-based amorphous coating in Example 1. Detailed Implementation

[0025] The present invention will be further described in detail below with reference to specific embodiments.

[0026] Titanium alloys and 316L substrate materials suffer from low hardness, poor corrosion resistance and wear resistance under high temperature, high pressure and strong corrosion environments, and typically require protective coatings in practical applications. In the embodiments and comparative examples of this invention, 316L is selected as the substrate.

[0027] Example 1

[0028] In this embodiment, the coating material is prepared and the coating is sprayed onto the substrate using the following method:

[0029] (1) First, 50g of Al2O3 reinforcing particles with a particle size of 40μm and 1g of paraffin particles were placed in a container. The container was placed in water and heated in a water bath at 60℃, and stirred to slowly melt the paraffin particles and attach them to the surface of the Al2O3 reinforcing particles. 50g of Al2O3 reinforcing particles with paraffin attached to the surface and 50g of Zr powder and Al powder with a particle size of 10μm were placed in a ball mill jar, where the molar ratio of Zr powder to Al powder was 1:1. Anhydrous ethanol was poured in until the mixed powder was submerged. Grinding balls were added at a ratio of 300g of grinding balls per 100g of material to be ball-milled. The ball mill jar was then evacuated and simultaneously filled with argon gas. This process was repeated 3 times to ensure an argon gas environment in the ball mill jar. The ball mill jar was then placed in a planetary ball mill and ball-milled at a speed of 300r / min for 8h. Then, the mixture was dried at 100℃ for 1h to obtain Al2O3 reinforcing particles coated with ZrAl powder.

[0030] (2) Place 50g of ZrAl powder coated Al2O3 reinforcing particles and 1g of paraffin particles in a container. Place the container in water and heat it in a water bath at 60°C. Stir to slowly melt the paraffin particles and attach them to the surface of the ZrAl powder coating layer. Place 50g of ZrAl powder coated Al2O3 reinforcing particles with paraffin attached to the surface and 50g of ZrAlCu amorphous powder with a particle size of 10μm into a ball milling jar. The atomic percentage of the ZrAlCu amorphous powder is 50% Zr, 30% Al, and 20% Cu. Pour anhydrous ethanol until the mixed powder is submerged. Add 300g of grinding balls for every 100g of material to be ball-milled. Then, evacuate the ball milling jar and fill it with argon gas. Circulate the jar three times to ensure that the ball milling jar is in an argon gas environment. Place the ball milling jar in a planetary ball mill and ball mill the powder at a speed of 300r / min for 8h. Then, the particles were dried at 100℃ for 1 hour to obtain Al2O3-reinforced particles coated with ZrAlCu powder.

[0031] (3) 40g of ZrAlCu powder-coated ceramic particles and 60g of ZrAlCuNi amorphous powder with a particle size of 10μm (the atomic percentage of ZrAlCuNi amorphous powder is: 60% Zr, 15% Al, 20% Cu, 5% Ni) and 1g of organic binder (paraffin: microcrystalline paraffin: methyl ethyl ketone = 6:1:0.5) were mixed in a ball mill at a speed of 400r / min for 5h. The mixture was then dried at 100℃ for 2h to obtain a particle-reinforced zirconium-based amorphous gradient composite coating material.

[0032] (4) The substrate surface is mechanically ground to smooth it, with a roughness Ra < 0.5, or surface contaminants are removed directly by corundum blasting, resulting in a surface roughness Ra 5.0-8.0. Then, it is cleaned and dried with alcohol. A supersonic flame spraying technique is used to spray the particle-reinforced zirconium-based amorphous gradient composite coating material onto the substrate surface to form a coating. During the spraying process, the oxygen flow rate is 40 m³ / s. 3 / h, kerosene flow rate is 20L / h, powder feeding rate is 20g / min, spraying distance is 300mm, spraying speed is 300m / s, coating thickness is 300μm.

[0033] Example 2

[0034] In this embodiment, the coating material is prepared and the coating is sprayed onto the substrate using the following method:

[0035] (1) First, 50g of Al2O3 reinforcing particles with a particle size of 65μm and 2g of paraffin particles were placed in a container. The container was placed in water and heated in a water bath at 65℃, and the paraffin particles were stirred to slowly melt and adhere to the surface of the Al2O3 reinforcing particles. 50g of Al2O3 reinforcing particles with paraffin adhering to the surface and 50g of Zr powder and Al powder with a particle size of 35μm were placed in a ball mill jar, where the molar ratio of Zr powder to Al powder was 1:1. Anhydrous ethanol was poured in until the mixed powder was submerged. Grinding balls were added at a ratio of 300g of grinding balls per 100g of material to be ball-milled. The ball mill jar was then evacuated and simultaneously filled with argon gas, and the process was repeated 3 times to ensure an argon gas environment in the ball mill jar. The ball mill jar was then placed in a planetary ball mill and ball-milled at a speed of 350r / min for 8.5h. Then, the mixture was dried at 150℃ for 1h to obtain Al2O3 reinforcing particles coated with ZrAl powder.

[0036] (2) Place 50g of ZrAl powder-coated Al2O3 reinforcing particles and 2g of paraffin particles in a container. Place the container in water and heat it in a water bath at 65°C. Stir the container to slowly melt the paraffin particles and attach them to the surface of the ZrAl powder coating. Place 50g of ZrAl powder-coated Al2O3 reinforcing particles with paraffin attached to the surface and 50g of ZrAlCu amorphous powder with a particle size of 30μm into a ball milling jar. The atomic percentage of the ZrAlCu amorphous powder is 60% Zr, 25% Al, and 15% Cu. Pour anhydrous ethanol until the mixed powder is submerged. Add 300g of grinding balls for every 100g of material to be ball-milled. Then, evacuate the ball milling jar and simultaneously fill it with argon gas. Circulate the jar three times to ensure that the ball milling jar is in an argon gas environment. Place the ball milling jar in a planetary ball mill and ball mill the powder at a speed of 350r / min for 8.5h. Then, the particles were dried at 150°C for 1 hour to obtain Al2O3-reinforced particles coated with ZrAlCu powder.

[0037] (3) 50g of ZrAlCu powder-coated ceramic particles and 50g of ZrAlCuNi amorphous powder with a particle size of 35μm (the atomic percentage of ZrAlCuNi amorphous powder is: 45% Zr, 15% Al, 30% Cu, 10% Ni) and 1g of organic binder (paraffin: microcrystalline paraffin: methyl ethyl ketone = 6.5:1.5:0.7) were mixed in a ball mill at a speed of 500r / min for 6h. The mixture was then dried at 100℃ for 2h to obtain a particle-reinforced zirconium-based amorphous gradient composite coating material.

[0038] (4) The substrate surface is mechanically ground to smooth it, with a roughness Ra < 0.5, or surface contaminants are removed directly by corundum blasting, resulting in a surface roughness Ra 5.0-8.0. Then, it is cleaned and dried with alcohol. A particle-reinforced zirconium-based amorphous gradient composite coating material is sprayed onto the substrate surface using supersonic flame spraying technology to form a coating. During the spraying process, the oxygen flow rate is 45 m³ / h. 3 / h, kerosene flow rate is 23L / h, powder feeding rate is 23g / min, spraying distance is 350mm, spraying speed is 250m / s, and coating thickness is 380μm.

[0039] Example 3

[0040] In this embodiment, the coating material is prepared and the coating is sprayed onto the substrate using the following method:

[0041] (1) First, 50g of Al2O3 reinforcing particles with a particle size of 90μm and 0.5g of paraffin particles were placed in a container. The container was placed in water and heated in a water bath at 70℃, and the paraffin particles were stirred to slowly melt and adhere to the surface of the Al2O3 reinforcing particles. 50g of Al2O3 reinforcing particles with paraffin adhering to the surface and 50g of Zr powder and Al powder with a particle size of 60μm were placed in a ball mill jar, where the molar ratio of Zr powder to Al powder was 1:1. Anhydrous ethanol was poured in until the mixed powder was submerged. Grinding balls were added at a ratio of 300g of grinding balls per 100g of material to be ball-milled. The ball mill jar was then evacuated and simultaneously filled with argon gas, and the process was repeated 3 times to ensure an argon gas environment in the ball mill jar. The ball mill jar was then placed in a planetary ball mill and ball-milled at a speed of 400r / min for 9h. Then, the mixture was dried at 200℃ for 1h to obtain Al2O3 reinforcing particles coated with ZrAl powder.

[0042] (2) Place 50g of ZrAl powder-coated ceramic particles and 0.5g of paraffin particles in a container. Place the container in water and heat it in a water bath at 70°C. Stir the container to slowly melt the paraffin particles and attach them to the surface of the ZrAl powder coating. Place 50g of ZrAl powder-coated Al2O3 reinforced particles with paraffin attached to the surface and 50g of ZrAlCu amorphous powder with a particle size of 50μm into a ball milling jar. The atomic percentage of the ZrAlCu amorphous powder is 45% Zr, 30% Al, and 25% Cu. Pour in anhydrous ethanol until the mixed powder is submerged. Add 300g of grinding balls for every 100g of material to be ball-milled. Then, evacuate the ball milling jar and fill it with argon gas. Circulate the jar three times to ensure that the ball milling jar is in an argon gas environment. Place the ball milling jar in a planetary ball mill and ball mill the powder at a speed of 400r / min for 9h. Then, the particles were dried at 200℃ for 1 hour to obtain Al2O3-reinforced particles coated with ZrAlCu powder.

[0043] (3) 50g of ZrAlCu powder-coated ceramic particles and 50g of ZrAlCuNi amorphous powder with a particle size of 60μm (the atomic percentage of ZrAlCuNi amorphous powder is: 55% Zr, 12% Al, 25% Cu, 8% Ni) and 1g of organic binder (paraffin: microcrystalline paraffin: methyl ethyl ketone = 7:2:1) were mixed in a ball mill at a speed of 600r / min for 8h. The mixture was then dried at 100℃ for 2h to obtain a particle-reinforced zirconium-based amorphous gradient composite coating material.

[0044] (4) The substrate surface is mechanically ground to achieve a surface roughness Ra < 0.5, or surface contaminants are removed directly by corundum blasting, resulting in a surface roughness Ra 5.0-8.0. The substrate is then cleaned and dried with alcohol. A supersonic flame spraying technique is used to apply a particle-reinforced zirconium-based amorphous gradient composite coating material to the substrate surface to form a coating. During the spraying process, the oxygen flow rate is 50 m³ / h. 3 / h, kerosene flow rate is 25L / h, powder feeding rate is 25g / min, spraying distance is 400mm, spraying speed is 350m / s, and coating thickness is 450μm.

[0045] Comparative Example 1

[0046] The coating material in this comparative example was prepared using the same method as in Example 2 and the coating was sprayed onto the substrate. The difference is that the coating material in this comparative example is ZrAlCuNi amorphous powder directly coated with Al2O3 reinforcing particles, without ZrAl and ZrAlCu layers.

[0047] Comparative Example 2

[0048] The coating material in this comparative example was prepared using the same method as in Example 1 and the coating was sprayed onto the substrate. The difference is that the coating material in this comparative example does not contain ZrAlCu amorphous components.

[0049] Comparative Example 3

[0050] The coating material in this comparative example was prepared using the same method as in Example 1 and the coating was sprayed onto the substrate. The difference is that the coating material in this comparative example is an Al2O3 reinforcing particle directly coated with a ZrAlCu amorphous powder layer, without ZrAl and ZrAlCuNi layers.

[0051] The coatings prepared in the examples and comparative examples were subjected to performance tests according to the following methods, and the results are shown in Table 1.

[0052] (1) Microhardness test of coating was performed using a digital Vickers microhardness tester with a test force of 0.98 N and a load time of 10 s. Ten areas were randomly selected for measurement, and the average hardness value was taken.

[0053] (2) The bonding strength of the coating was tested. The bonding strength of the zirconium-based amorphous coating on the substrate was determined by an electronic universal testing machine. Commercial FM1000 adhesive was used to bond the coating surface and the loading fixture. The test speed was set to 0.021 mm / s, the maximum applied load was recorded, and the bonding strength was calculated.

[0054] (3) Conduct corrosion resistance electrochemical tests on the coating. Use an electrochemical workstation to conduct corrosion tests. The corrosion solution is 20% H2SO4. Calculate the corrosion rate by testing the polarization curve of the coating.

[0055] (4) The coating was subjected to a wear resistance test. The coating was subjected to a wear test using a reciprocating friction and wear tester. The friction pair was a steel ball with a diameter of 6 mm, the load was 50 N, the friction rate was 3 mm / s, the sliding length was 3 mm, and the sliding time was 60 min. The wear rate was obtained.

[0056] Table 1. Mechanical and corrosion / wear properties of the zirconium-based amorphous coatings prepared in the examples and comparative examples.

[0057]

[0058] As shown in Table 1, the coating prepared by the method of the present invention has significantly improved bonding strength, hardness, and bonding strength compared to the comparative example.

[0059] Compared with Example 2, Comparative Example 1 showed significant differences in corrosion and wear performance. The main reason is that the coating of Comparative Example 1 lacked the ZrAl and ZrAlCu layers. The Al2O3 reinforcing particles were directly ball-milled and mixed with the zirconium-based amorphous powder, resulting in direct contact between Al2O3 and the zirconium-based amorphous powder. The two could not form a metallurgically bonded interface layer, but rather a mechanical bond. The Al2O3 particles were easily detached during the wear test, resulting in a significant difference in wear resistance between Comparative Example 1 and Example 2.

[0060] In the embodiments, Al2O3 reinforcing particles can undergo an interfacial reaction with the ZrAl alloy layer, strengthening the interfacial bonding ability and effectively transferring stress, thereby improving the fracture strength of the alloy. Through multiple gradient composite processes, a transition from crystalline reinforcing particles to an amorphous layer is formed, allowing for better composite between the reinforcing particles and the amorphous layer, thus improving the bonding strength between the coating and the substrate. Therefore, Comparative Example 1, lacking a ZrAl layer, exhibits poor mechanical properties.

[0061] The lack of a ZrAlCu amorphous coating layer in Comparative Example 2 leads to a decrease in its overall performance. This is because the direct bonding between the ZrAl alloy and the ZrAlCuNi amorphous material does not involve a gradient effect of elements, making it easy for cracks to appear between the ZrAl alloy and the ZrAlCuNi amorphous material. This also makes the coating of Al2O3 reinforcing particles unstable and prone to brittle detachment.

[0062] In Comparative Example 3, the Al2O3 ceramic particles were not coated with ZrAl powder, but only with an amorphous ZrAlCu powder layer. This resulted in contact between the Al2O3 and ZrAlCu amorphous phases, creating a direct transition from the crystalline to the amorphous phase of the ceramic particles. This direct transition can lead to weak interfacial bonding: firstly, the direct contact between the crystalline and amorphous phases increases interfacial instability, potentially affecting the bonding strength between the ceramic particles and the powder layer, leading to poor adhesion and impacting the overall mechanical and wear resistance of the coating. Secondly, the direct transition can also alter the structure and properties of the Al2O3 ceramic particles. In the amorphous environment, the ceramic particles may experience crystal structure damage or grain size changes, affecting their original performance stability. Because the direct transition from the crystalline to the amorphous phase can cause interfacial bonding and ceramic particle performance instability issues, it ultimately affects the overall performance of the coating, including mechanical and wear resistance properties.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating, characterized in that: The preparation method includes the following steps: (1) First, place Al2O3 reinforcing particles and paraffin particles in a container, place the container in water for water bath heating, and stir to slowly melt the paraffin particles and attach them to the surface of Al2O3 reinforcing particles. Then, put the Al2O3 reinforcing particles with paraffin attached to the surface, Zr powder and Al powder into a ball mill jar, and pour anhydrous ethanol into the ball mill jar until the mixed powder is submerged. Then, ball milling is performed in an argon atmosphere, and then drying is performed to obtain Al2O3 reinforcing particles coated with ZrAl powder. (2) Place the Al2O3 reinforcing particles coated with ZrAl powder in step (1) and the paraffin particles in a container, place the container in water for water bath heating, and stir to slowly melt the paraffin particles and attach them to the surface of the ZrAl powder coating layer. Place the Al2O3 reinforcing particles coated with ZrAl powder and the ZrAlCu amorphous powder into a ball mill jar, pour in anhydrous ethanol until the mixed powder is submerged, and then perform cyclic ball milling in an argon atmosphere. Then perform drying treatment to obtain Al2O3 reinforcing particles coated with ZrAlCu powder. (3) The Al2O3 reinforcing particles coated with ZrAlCu powder obtained in step (2) are mixed with ZrAlCuNi amorphous powder and organic binder in a ball mill, and then dried to obtain an Al2O3 particle-reinforced zirconium-based amorphous gradient composite coating material with a gradient structure. (4) The substrate is ground, sandblasted and ultrasonically cleaned, and then cleaned and dried with alcohol. Then, the particle-reinforced zirconium-based amorphous gradient composite coating material obtained in step (3) is sprayed onto the substrate surface to form a coating using supersonic flame spraying technology.

2. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1, characterized in that: In step (1), the particle size of Al2O3 reinforcing particles is 40~90μm, the particle size of Zr powder and Al powder is 10~60μm, the molar ratio of Zr powder and Al powder is Zr powder:Al powder = 1:1, and the mass ratio of Al2O3 reinforcing particles with paraffin attached to the surface to the total mass of Zr powder and Al powder is 1:

1.

3. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1, characterized in that: In step (2), the mass ratio of Al2O3 reinforced particles coated with ZrAl powder to ZrAlCu amorphous powder is 1:

1. The particle size of ZrAlCu amorphous powder is 10~50μm. The atomic percentage of ZrAlCu amorphous powder is: 45~60% Zr, 20~30% Al, and 15%~25% Cu.

4. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to any one of claims 1-3, characterized in that: In steps (1) and (2), the mass of paraffin particles added is 1-4% of the total mass of Al2O3 reinforcing particles and paraffin particles, and the water bath heating temperature is 60-70℃. The ball milling conditions are as follows: the mass ratio of the material to be milled to the grinding balls is 1:3, the planetary ball mill is used to mix the powder at a speed of 300-400 r / min, the ball milling time is 8-9h, the drying temperature is 100-200℃, and the drying time is 1h.

5. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1, characterized in that: In step (3), the atomic percentage of the ZrAlCuNi amorphous powder is: 45~60% Zr, 10~15% Al, 20~30% Cu, 5~10% Ni, the particle size of the ZrAlCuNi amorphous powder is 10~60μm, the mass ratio of the Al2O3 reinforcing particles coated with ZrAlCu powder to the mass of ZrAlCuNi amorphous powder is 1~2:1~3; the total mass ratio of the added Al2O3 reinforcing particles coated with ZrAlCu powder and the ZrAlCuNi amorphous powder to the organic binder is 100:1, the ball milling speed is 400~600 r / min, the ball milling time is 5~8h, and the drying is carried out in a vacuum drying oven at a drying temperature of 100℃ for 2h.

6. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1 or 5, characterized in that: The organic adhesive is a water-soluble adhesive composed of paraffin wax, microcrystalline wax, and methyl ethyl ketone, wherein the mass ratio of paraffin wax: microcrystalline wax: methyl ethyl ketone is 6~7:1~2:0.5~1.

7. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1, characterized in that: In step (4), during the supersonic flame spraying process, the oxygen flow rate is 40~50 m³ / h. 3 / h, kerosene flow rate is 20~25 L / h, powder feeding rate is 20~25 g / min, spraying distance is 300~400 mm, and spraying speed is 250~350 mm / s.

8. The method for preparing a particle-reinforced zirconium-based amorphous gradient composite coating according to claim 1 or 7, characterized in that: The coating thickness formed by spraying the particle-reinforced zirconium-based amorphous gradient composite material onto the substrate is 300~450μm.

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