Preparation method of anti-oxidation coating on surfaces of molybdenum and molybdenum alloy

Abstract

The invention belongs to the technical field of metal surface treatment, and relates to a preparation method of a molybdenum and molybdenum alloy surface anti-oxidation coating. The invention provides a preparation method of an anti-oxidation coating on the surface of molybdenum and molybdenum alloy. The preparation method comprises the steps that Al2O3 powder, Y2O3 powder, TiC powder, CeO2 powder and Si powder are subjected to ball milling and then dried, and a permeating agent is obtained; polishing the substrate to remove a surface oxide layer, and then carrying out heat preservation treatment to obtain a stabilized coating; the permeating agent is prepared from the following effective components in percentage by mass: 10 to 30 percent of Al2O3 powder, 1 to 3 percent of Y2O3 powder, 4 to 8 percent of TiC powder, 0.8 to 2 percent of CeO2 powder and the balance of Si powder, and the matrix is pure molybdenum or molybdenum alloy. The invention aims to solve the technical problem that an anti-oxidation coating on the surface of molybdenum and molybdenum alloy is easy to crack and fall off under thermal shock.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal surface treatment, and relates to a method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloys. Background Technique

[0002] Refractory metals have characteristics such as high melting point, good processing performance, excellent corrosion resistance and mechanical properties. Among them, molybdenum has good thermal conductivity and low thermal deformation. It still has good mechanical properties at 1500 °C and is considered to be one of the most promising structural materials. However, molybdenum is prone to generate volatile MoO3 at about 600 °C. As the temperature increases, the volatilization rate of MoO3 increases, reducing its mechanical properties at high temperatures, which limits the use of molybdenum and molybdenum alloys at high temperatures. At present, there are mainly two methods to improve the antioxidant performance of molybdenum and molybdenum alloys, namely alloying and antioxidant coatings. By adding antioxidant elements through alloying, the mechanical properties of the material can be improved, and an oxide film is formed on the surface of the molybdenum alloy at high temperature to prevent the rate of oxygen element from entering the matrix, thereby improving the antioxidant performance. However, when the content of alloying elements is relatively high, the processing performance of the material will be reduced; preparing a coating on the alloy surface is a very effective method, which can significantly improve the antioxidant performance of the alloy without changing the mechanical properties of the alloy. During the design of the coating, the bonding situation between the coating and the matrix needs to be considered to ensure that the coating does not peel off or crack at high temperatures.

[0003] Mo-Si binary alloy can generate SiO2 at high temperature, and the higher the Si element content, the lower the oxidation rate of the alloy. The influence of low content of Al and Si on the antioxidant performance of Mo alloy at high temperature was found. After adding Al element, a relatively thin oxide layer of Al2O3 appears on the alloy surface. The addition of Si element is beneficial to the increase of the oxide film thickness, but the phenomenon of weight loss still cannot be changed. Aluminide coatings have low cost and relatively simple processes. Aluminide coatings have little degradation of the mechanical properties of the matrix and good antioxidant performance, but when subjected to thermal shock, the coating is prone to peel off and crack from the matrix, thus affecting the use of the alloy. Summary of the Invention

[0004] The purpose of the present invention is to solve the technical problem that the antioxidant coating on the surface of molybdenum and molybdenum alloys is prone to cracking and peeling under thermal shock, resulting in coating failure.

[0005] In response to this, the present invention provides a method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloys to solve this need in the art.

[0006] On the one hand, the present invention relates to a method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloys, which includes: ball-milling and drying Al2O3 powder, Y2O3 powder, TiC powder, CeO2 powder and Si powder to obtain a penetrant; The substrate is polished to remove the surface oxide layer and then subjected to heat preservation treatment to obtain a stabilized coating; By mass percentage, the active components in the penetrant are composed of 10-30% Al2O3 powder, 1-3% Y2O3 powder, 4-8% TiC powder, 0.8-2% CeO2 powder and the balance Si powder; The substrate is pure molybdenum or a molybdenum alloy.

[0007] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the heat preservation treatment is to keep the temperature at 1100-1300 °C for 20-25 h in an inert gas atmosphere.

[0008] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the inert gas is nitrogen or argon.

[0009] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the heat preservation treatment is to keep the temperature at 1150-1250 °C for 10-15 h in a nitrogen atmosphere, then keep the temperature at 1550-1650 °C for 2-5 h, and finally keep the temperature at 600-800 °C for 20-30 h.

[0010] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the penetrant further contains a penetration promoter; By mass percentage, the active components in the penetrant are composed of 10-30% Al2O3 powder, 1-3% Y2O3 powder, 4-8% TiC powder, 0.8-2% CeO2 powder, 1-5% of the penetration promoter and the balance Si powder.

[0011] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the penetration promoter is NaF.

[0012] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the ball milling rate is 100-300 r / min and the ball milling time is 1-3 h.

[0013] Furthermore, in the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy provided by the present invention, the ball-to-material ratio of the ball milling is 5-10:1.

[0014] On the other hand, the present invention relates to a molybdenum and molybdenum alloy with an antioxidant coating, which is prepared by using the method for preparing the antioxidant coating on the surface of molybdenum and molybdenum alloy described above.

[0015] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages: The present invention provides a method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloys. Through a chemical reaction between a penetrant with a specific ratio and a molybdenum or molybdenum alloy substrate in an inert gas atmosphere, a dense antioxidant coating is formed. Meanwhile, by combining substrate pretreatment and the use of a penetration promoter, the bonding strength between the coating and the substrate is enhanced, and the formation speed and uniformity of the coating are improved. First, it significantly improves the antioxidant performance of molybdenum and molybdenum alloys at high temperatures and extends the service life of the materials. Second, through a specific penetrant formulation and heat preservation treatment conditions, a good bonding strength is formed between the coating and the substrate, and it is not easy to crack and fall off even under thermal shock, solving the problem that traditional antioxidant coatings are prone to cracking and falling off. In addition, without changing the mechanical properties of the molybdenum and molybdenum alloy substrates, this method significantly improves their antioxidant performance. This method has a wide range of applications and is applicable not only to pure molybdenum substrates but also to various molybdenum alloy substrates. Special processes such as segmented heat preservation treatment help to form a more stable and uniform coating structure and improve the stability of the materials at high temperatures. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0017] Figure 1 The surface morphology of the coating after the antioxidant performance test under thermal shock of the specimen provided in Example 1.

[0018] Figure 2 The surface morphology of the coating after the antioxidant performance test under thermal shock of the specimen provided in Comparative Example 1.

[0019] Figure 3 The surface morphology of the coating after the antioxidant performance test under thermal shock of the specimen provided in Comparative Example 2.

[0020] Figure 4 The surface morphology of the coating after the antioxidant performance test under thermal shock of the specimen provided in Comparative Example 3. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] Next, the technical solutions of the present invention will be described in conjunction with the embodiments. However, the present invention is not limited to the following embodiments. The experimental methods and detection methods described in each embodiment are conventional methods unless otherwise specified; the reagents and materials can be obtained in the market unless otherwise specified. The percentages in the following embodiments are mass percentages unless otherwise specified. The ratios in the following embodiments are mass ratios unless otherwise specified.

[0022] In the following examples, the purity of each powder raw material used is not less than 99.8%.

[0023] Example 1 This example provides the process of preparing an antioxidant coating on the surface of pure molybdenum by pack cementation.

[0024] The pure molybdenum substrate was wire cut into a metal plate of 50mm×50mm×3mm on a metallographic grinding and polishing machine, and then polished with silicon carbide sandpapers of 240 mesh, 400 mesh, 600 mesh, 1000 mesh and 2000 mesh in sequence to remove the surface oxide layer. Then, in an ultrasonic cleaner, it was cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and washed repeatedly for 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain a sample.

[0025] By mass percentage, 10% of Al2O3 powder, 1% of Y2O3 powder, 4% of TiC powder, 0.8% of CeO2 powder, 1% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet grinding with anhydrous ethanol as the medium, the ball-to-material ratio was 8:1, the rotation speed was 150 r / min, and the ball milling time was 2 h. Finally, it was placed in a vacuum drying oven and dried at 80°C for 8 h to obtain the infiltration material.

[0026] The sample was buried in the infiltration material and held at 1200°C for 24 h in nitrogen to obtain molybdenum with an antioxidant coating.

[0027] Example 2 This example provides the process of preparing an antioxidant coating on the surface of pure molybdenum by pack cementation.

[0028] The pure molybdenum substrate was wire cut into a metal plate of 50mm×50mm×3mm on a metallographic grinding and polishing machine, and then polished with silicon carbide sandpapers of 240 mesh, 400 mesh, 600 mesh, 1000 mesh and 2000 mesh in sequence to remove the surface oxide layer. Then, in an ultrasonic cleaner, it was cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and washed repeatedly for 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain a sample.

[0029] By mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 1.5% of CeO2 powder, 3% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet grinding with anhydrous ethanol as the medium, the ball-to-material ratio was 8:1, the rotation speed was 150 r / min, and the ball milling time was 2 h. Finally, it was placed in a vacuum drying oven and dried at 80°C for 8 h to obtain the infiltration material.

[0030] The sample was buried in the infiltration material and held at 1200°C for 24 h in nitrogen to obtain molybdenum with an antioxidant coating.

[0031] Example 3 This embodiment provides a process for preparing an antioxidant coating on the surface of pure molybdenum by pack cementation method.

[0032] The pure molybdenum substrate was wire cut into a metal plate of 50mm×50mm×3mm on a metallographic polishing machine, and then polished successively with 240-mesh, 400-mesh, 600-mesh, 1000-mesh and 2000-mesh silicon carbide sandpapers to remove the surface oxide layer. Then, in an ultrasonic cleaning machine, it was cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and repeatedly cleaned 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain a sample.

[0033] By mass percentage, 30% of Al2O3 powder, 3% of Y2O3 powder, 8% of TiC powder, 2% of CeO2 powder, 3% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet milling with anhydrous ethanol as the medium, the ball-to-material ratio was 8:1, the rotation speed was 150r / min, and the ball milling time was 2h. Finally, it was placed in a vacuum drying oven and dried at 80°C for 8h to obtain the infiltration material.

[0034] The sample was buried in the infiltration material and kept at 1200°C for 24h in nitrogen to obtain molybdenum with an antioxidant coating.

[0035] Example 4 This embodiment provides a process for preparing an antioxidant coating on the surface of pure molybdenum by pack cementation method.

[0036] The pure molybdenum substrate was wire cut into a metal plate of 50mm×50mm×3mm on a metallographic polishing machine, and then polished successively with 240-mesh, 400-mesh, 600-mesh, 1000-mesh and 2000-mesh silicon carbide sandpapers to remove the surface oxide layer. Then, in an ultrasonic cleaning machine, it was cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and repeatedly cleaned 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain a sample.

[0037] By mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 1.5% of CeO2 powder, 3% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet milling with anhydrous ethanol as the medium, the ball-to-material ratio was 8:1, the rotation speed was 150r / min, and the ball milling time was 2h. Finally, it was placed in a vacuum drying oven and dried at 80°C for 8h to obtain the infiltration material.

[0038] The sample was buried in the infiltration material, kept at 1200°C for 12h in nitrogen, then at 1600°C for 4h, and finally at 700°C for 24h to obtain molybdenum with an antioxidant coating.

[0039] Example 5 This embodiment provides a process for preparing an antioxidant coating on the surface of molybdenum alloy by pack cementation method.

[0040] The TZC alloy was wire-cut into a metal plate of 50 mm × 50 mm × 3 mm on a metallographic grinding and polishing machine, and then polished successively with silicon carbide sandpapers of 240 mesh, 400 mesh, 600 mesh, 1000 mesh and 2000 mesh to remove the surface oxide layer. Then, in an ultrasonic cleaner, it was cleaned with acetone, ethanol and deionized water for 15 min respectively, and repeatedly cleaned 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain the sample.

[0041] By mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 1.5% of CeO2 powder, 3% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet grinding with anhydrous ethanol as the medium, the ball-to-material ratio was 5:1, the rotation speed was 100 r / min, and the ball milling time was 1 h. Finally, it was placed in a vacuum drying oven and dried at a constant temperature of 80 °C for 8 h to obtain the infiltration material.

[0042] The sample was buried in the infiltration material and kept at 1200 °C for 24 h in nitrogen to obtain the TZC alloy with an antioxidant coating.

[0043] Example 6 This example provides the process of preparing an antioxidant coating on the surface of a molybdenum alloy by the pack cementation method.

[0044] The TZM alloy was wire-cut into a metal plate of 50 mm × 50 mm × 3 mm on a metallographic grinding and polishing machine, and then polished successively with silicon carbide sandpapers of 240 mesh, 400 mesh, 600 mesh, 1000 mesh and 2000 mesh to remove the surface oxide layer. Then, in an ultrasonic cleaner, it was cleaned with acetone, ethanol and deionized water for 15 min respectively, and repeatedly cleaned 3 times. Finally, it was dried in a vacuum constant temperature drying oven to obtain the sample.

[0045] By mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 1.5% of CeO2 powder, 3% of NaF and the balance of Si powder were taken for batching. A planetary ball mill was used for wet grinding with anhydrous ethanol as the medium, the ball-to-material ratio was 10:1, the rotation speed was 300 r / min, and the ball milling time was 3 h. Finally, it was placed in a vacuum drying oven and dried at a constant temperature of 80 °C for 8 h to obtain the infiltration material.

[0046] The sample was buried in the infiltration material and kept at 1200 °C for 24 h in argon to obtain the TZM alloy with an antioxidant coating.

[0047] Comparative Example 1 This comparative example aims to illustrate the role of the components in the infiltration material.

[0048] This comparative example is the same as Example 2, except that when preparing the infiltration material, by mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 3% of NaF, and the balance of Si powder are taken for batching.

[0049] Comparative Example 2 This comparative example aims to illustrate the functions of the components in the infiltration material.

[0050] This comparative example is the same as Example 2, except that when preparing the infiltration material, by mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of Ti powder, 1.5% of CeO2 powder, 3% of NaF, and the balance of Si powder are taken for batching.

[0051] Comparative Example 3 This comparative example aims to illustrate the functions of the component ratios in the infiltration material.

[0052] This comparative example is the same as Example 2, except that when preparing the infiltration material, by mass percentage, 20% of Al2O3 powder, 2% of Y2O3 powder, 6% of TiC powder, 10% of CeO2 powder, 3% of NaF, and the balance of Si powder are taken for batching.

[0053] The products prepared in Examples 1 - 6 and Comparative Examples 1 - 3 are subjected to coating adhesion tests and oxidation resistance tests under thermal shock.

[0054] Coating adhesion test: The acoustic emission detection technology of a coating adhesion automatic scratch tester (Lanzhou Zhongke Kaihua WS - 2005) is used to measure the bonding strength between the coating and the substrate. The acoustic emission detection technology is one of the main detection methods of the coating adhesion automatic scratch tester; when the coating of the material is scratched or peeled off by the scratching needle, a weak acoustic signal will be emitted, and the instrument can monitor the bonding strength between the coating and the substrate in real time by capturing these acoustic signals; the acoustic emission detection technology has high sensitivity and can accurately judge at what pressure the coating will peel off or break. During the experiment, it operates in a dynamic load mode, with a loading rate of 30 N / min, a test load of 30 N, and a scratch length of 3 mm.

[0055] Oxidation resistance test under thermal shock: In air, a box furnace is used to conduct the oxidation resistance test under thermal shock at 1200°C. After heating the box furnace to 1200°C, the specimens at room temperature are placed into the furnace. After being exposed for 1 h, 2 h, 3 h, 4 h, 5 h, and 6 h respectively, the specimens are taken out and naturally cooled to room temperature, and then the mass change of the specimens is weighed. After 6 h, the specimens naturally cooled to room temperature are placed into the furnace again, and the mass change of the specimens is weighed every 2 h. After oxidizing at 1200°C for 100 h (the oxidation duration in the furnace), the coating adhesion is measured again.

[0056] The test results are shown in Table 1. Among them, the antioxidant failure time is the exposure duration when the mass loss exceeds 5 mg / cm 2 , and the maximum mass loss is the mass loss measured at antioxidant failure or the maximum mass loss during oxidation from 0 to 100 h.

[0057] Table 1 Test Results

[0058] As can be seen from Table 1, the samples of Examples 1 to 6 all showed relatively high values of the bonding strength before oxidation, ranging from 10.1 N to 14.1 N respectively. Although the bonding strength decreased after oxidation, it still remained in the range of 8.4 N to 13.4 N, indicating a strong bonding strength between the coating and the substrate. In terms of antioxidant performance, after the samples of all examples underwent a thermal shock test at 1200 °C for up to 100 hours, no antioxidant failure occurred, and the maximum mass loss was controlled between -3.5 mg / cm 2 and -2.2 mg / cm 2 , indicating that these samples have excellent antioxidant performance. In contrast, the samples of Comparative Examples 1 to 3 all showed relatively poor results in terms of coating bonding strength and antioxidant performance. The sample of Comparative Example 1 had a bonding strength of 7.9 N before oxidation, the coating cracked after oxidation, the antioxidant failure time was only 44 hours, and the maximum mass loss reached -8.7 mg / cm 2 . The sample of Comparative Example 2 had a bonding strength of 8.9 N before oxidation. Although the bonding strength decreased slightly after oxidation, the cracking situation was not clearly stated. However, its antioxidant failure time was extended to 86 hours, and the maximum mass loss was -5.2 mg / cm 2 , still inferior to that of the examples. The sample of Comparative Example 3 had a bonding strength of 8.6 N before oxidation, the coating also cracked after oxidation, the antioxidant failure time was 94 hours, and the maximum mass loss was -6.9 mg / cm 2 . Although it was slightly better than Comparative Examples 1 and 2, it still could not compare with the examples.

[0059] Figure 1 Figure 24 shows the surface morphology of the coating after the antioxidant performance test under thermal shock for the specimen provided in Example 1. Figure 2 Figure 26 shows the surface morphology of the coating after the antioxidant performance test under thermal shock for the specimen provided in Comparative Example 1. Figure 3 Figure 28 shows the surface morphology of the coating after the antioxidant performance test under thermal shock for the specimen provided in Comparative Example 2. Figure 4 Figure 30 shows the surface morphology of the coating after the antioxidant performance test under thermal shock for the specimen provided in Comparative Example 3. Figure 1It can be seen that after the oxidation resistance performance test of the coating provided by the present invention under thermal shock, it is still dense. Except for very few irregular pores, microcracks are hardly visible. From Figures 2 to 4 It can be seen that for the coating obtained due to the absence of any component or improper proportioning, after the oxidation resistance performance test under thermal shock, due to its inability to withstand the release of thermal stress, the formation of long and narrow pores is caused. As can be seen from the above figure, a method for preparing an oxidation-resistant coating on the surface of molybdenum and molybdenum alloy provided by the present invention can preferably solve the technical problem that the oxidation-resistant coating on the surface of molybdenum and molybdenum alloy is prone to cracking and peeling under thermal shock ( Figure 1 ), and the absence of any component or improper proportioning will cause the problem of cracking ( Figure 2 , Figure 3 and Figure 4 shown). In summary, through specific penetrant components, molybdenum and molybdenum alloy samples with excellent oxidation resistance and coating adhesion were successfully prepared in Examples 1 to 6. However, in Comparative Examples 1 to 3, due to improper penetrant components or proportions, the coating performance decreased significantly, and the problem of coating cracking occurred under thermal shock.

[0060] As described above, the basic principle, main features and advantages of the present invention are preferably described. The above embodiments and the description are only descriptions of the preferred embodiments of the present invention. The present invention is not limited by the above embodiments. Without departing from the spirit and scope of the present invention, various changes and improvements made by those of ordinary skill in the art to the technical solution of the present invention shall fall within the protection scope determined by the present invention.

Claims

1. A method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloys, characterized in that, Comprising: After ball-milling and drying Al2O3 powder, Y2O3 powder, TiC powder, CeO2 powder and Si powder, an infiltrant is obtained. After the substrate is polished to remove the surface oxide layer and then subjected to heat preservation treatment, a stabilization coating is obtained. By mass percentage, the active components in the infiltrant are composed of 10-30% Al2O3 powder, 1-3% Y2O3 powder, 4-8% TiC powder, 0.8-2% CeO2 powder and the balance Si powder. The substrate is pure molybdenum or a molybdenum alloy.

2. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 1, characterized in that, The heat preservation treatment is to keep the temperature at 1100-1300 °C for 20-25 h in an inert gas atmosphere.

3. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 2, characterized in that, The inert gas is nitrogen or argon.

4. The preparation method of the anti-oxidation coating on the surface of molybdenum and molybdenum alloy according to claim 1, wherein, The heat preservation treatment is to keep the temperature at 1150-1250 °C for 10-15 h in a nitrogen atmosphere first, then keep the temperature at 1550-1650 °C for 2-5 h, and finally keep the temperature at 600-800 °C for 20-30 h.

5. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 1, wherein The infiltrant also contains a penetration promoter. By mass percentage, the active components in the infiltrant are composed of 10-30% Al2O3 powder, 1-3% Y2O3 powder, 4-8% TiC powder, 0.8-2% CeO2 powder, 1-5% of the penetration promoter and the balance Si powder.

6. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 5, characterized in that The penetration promoter is NaF.

7. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 1, characterized in that, The rate of the ball-milling is 100-300 r / min, and the time of the ball-milling is 1 h-3 h.

8. The preparation method of the antioxidant coating on the surface of molybdenum and molybdenum alloy according to claim 7, wherein The ball-to-material ratio of the ball-milling is 5-10:

1.

9. A molybdenum and molybdenum alloy with an antioxidant coating, characterized in that, Prepared by the method for preparing an antioxidant coating on the surface of molybdenum and molybdenum alloy according to any one of claims 1-8.

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