Ta-based refractory metal surface composite gradient structure coating and preparation method thereof

Abstract

The application belongs to the technical field of thermal protection coating materials, and discloses a Ta-based refractory metal surface composite gradient structure coating and a preparation method thereof. The composite gradient structure coating comprises, from inside to outside on the Ta base, a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer; the composition of the primer layer is metal or metal carbide; the composition of the diffusion barrier layer is metal carbide; the composition of the transition layer is metal carbide and Re; the content of the metal carbide in the transition layer decreases in a gradient from inside to outside, and the content of Re increases in a gradient; and the thermal protection layer comprises, from inside to outside, a Re layer, an Ir layer and an HfO2-Y2O3 layer. The high vacuum magnetron sputtering technology is adopted to form the coating with the composite gradient structure on the Ta-based refractory metal; and the coating prepared by the application is closely combined between layers and with the base, effectively reduces the formation of volatile oxides of iridium elements, and thus improves the high-temperature protection performance of the whole coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of thermal protection coating materials, and particularly relates to a Ta-based refractory metal surface composite gradient structure coating and a preparation method thereof. BACKGROUND

[0002] The hypersonic vehicle refers to a vehicle that can cruise at a speed of more than 5 Mach and reach a battlefield 5000 kilometers away within 1 hour, has good concealment, strong penetration ability, high combat effectiveness and extensive combat space, and can realize strategic goals such as precision strike, rapid transportation and long-range real-time reconnaissance, and has important research significance.

[0003] Compared with the service environment of a traditional vehicle, the service environment of a hypersonic vehicle is under the condition of atmospheric reentry, and the temperature of the nose cone and the leading edge of the hypersonic vehicle can be more than 1600 DEG C. The thermal environment of the hypersonic vehicle includes super-high temperature of more than 2000 DEG C, large thermal gradient and stress, a gas flow with a high chemical activity of more than 10 MW·m -2 of the hypersonic vehicle, and complex thermal-mechanical load. Therefore, the material used in these areas must be able to withstand super-high temperature and strong heat flux related to large mechanical stress. Therefore, it is very important to develop a thermal protection system with good oxidation resistance, thermal shock resistance, ablation resistance and dimensional stability.

[0004] Tantalum and tantalum alloy have high melting point, good corrosion resistance, excellent high-temperature strength, good processing performance, weldability, low plastic / brittle transition degree and excellent dynamic mechanical properties, and are ideal structural materials working in an environment of 1600 DEG C to 1800 DEG C and have very important applications in the field of aerospace. Although tantalum and tantalum alloy have excellent high-temperature mechanical properties, they have poor high-temperature oxidation resistance. Metallic tantalum will generate Ta2O5 by accelerated oxidation at a temperature of more than 500 DEG C, and the oxidation will be more serious with the increase of temperature until complete powdering and destruction, which limits the application of tantalum and tantalum alloy. In order to improve the service life of the alloy at high temperature, the most effective method is to prepare a protective coating on the surface of the alloy. The surface coating can have the advantages of low oxygen permeability, good chemical and physical compatibility and stability, low volatility, good thermal expansion coefficient matching and bonding ability, high-temperature self-healing ability and no influence on the original good mechanical properties of the tantalum alloy substrate, and is the best method to solve the problems of high-temperature mechanical properties and oxidation resistance of tantalum alloy.

[0005] Metal iridium has good corrosion resistance, is insoluble in sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid and sodium hydroxide melt, has good chemical stability, very low oxygen permeability, and basically remains unchanged with the increase of temperature, and has excellent high-temperature mechanical stability, and at 1800 DEG C, the oxygen permeability of 1 mu m of Ir is equivalent to 1 mm of SiO2; Therefore, Ir is considered to be one of the most ideal high-temperature oxidation resistant coating materials above 1800 DEG C.

[0006] Although Ir coating is applied to high-temperature oxidation resistant coating because of very low oxygen permeability, however, there are still some problems in the use of pure Ir, which has a great influence on its service life. Iridium coating mainly faces two problems during service: (1) the phenomenon of Ir coating micropore diffusion and aggregation along the grain boundary will lead to the formation of rapid diffusion path of grain boundary, which provides the shortest diffusion path for oxygen elements and matrix elements, and the coating fails in advance. (2) Ir coating has defects in high-temperature oxidation characteristics. On the one hand, iridium is oxidized and volatilized in the form of IrO2 and IrO3 when the temperature is higher than 1100 DEG C, which leads to continuous thinning of the coating; On the other hand, Ir has high catalytic activity and low thermal emissivity, which makes the surface temperature of iridium coating rise sharply, and aggravates the oxidation and ablation of iridium. Therefore, it is necessary to modify the Ir coating according to the organizational structure characteristics and high-temperature oxidation characteristics of Ir, and improve the high-temperature oxidation resistance of the coating. SUMMARY

[0007] In order to solve the above technical problems, the present application provides a Ta-based refractory metal surface composite gradient structure coating and a preparation method thereof.

[0008] The Ta-based refractory metal surface composite gradient structure coating and the preparation method thereof of the present application are realized by the following technical scheme:

[0009] In the exploration process, it is found that if the preparation process is directly changed to optimize the organizational structure of the coating to improve the high-temperature oxidation resistance of the Ir coating, because the working temperature of Ir is much higher than its recrystallization temperature, the grain of Ir coating grows rapidly during use, and the grain boundary structure cannot remain stable for a long time, and changing the organizational structure cannot slow down the oxidation and volatilization rate of Ir coating, therefore, simply changing the preparation process to optimize the organizational structure of Ir coating has limited improvement on the oxidation resistance life of Ir coating.

[0010] If the performance of the Ir coating is improved by directly adopting the mode of arranging a ceramic coating with high melting point, low thermal conductivity and high radiation on the surface of the Ir coating, the ceramic coating can directly block the contact between iridium and the external environment and thus reduce the surface temperature of the coating, but some ceramic coatings such as HfO2 and ZrO2 will generate volume change and internal stress during the heating process due to solid phase change, which will result in poor combination between the ceramic layer and the Ir coating and finally cause the ceramic layer to peel off, or the micro-pore and crack defects generated during the service period of the ceramic coating cannot be healed and the defects will continuously grow until the protective effect of the ceramic coating on the Ir coating is lost, that is, it is difficult to effectively improve the high-temperature oxidation resistance of the Ir coating by arranging the ceramic coating.

[0011] If the performance of the Ir coating is improved by directly adopting the mode of alloying modification treatment of the Ir coating surface by alloying elements such as Hf, Zr, Ta and Al, so that these alloying elements are continuously oxidized to generate a dense refractory oxide outer layer in the high-temperature oxidizing environment, thereby protecting the Ir coating, but after the alloying elements are oxidized, a relatively dense oxide outer layer is generated in situ, and the oxide layer is prone to cracking and peeling due to the mismatch of physical parameters such as thermal expansion coefficient, and thus loses the protective effect.

[0012] Therefore, based on the above research, in order to prolong the service life of the coating under working conditions and improve the bonding strength between the coating and the substrate, the present application provides a Ta-based refractory metal surface composite gradient structure coating, which is arranged on the Ta substrate and comprises a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer arranged in the Ta substrate from inside to outside in turn.

[0013] The composition of the primer layer is metal or metal carbide, and the bias voltage of the primer layer gradually decreases from inside to outside on the Ta substrate, and the change of the bias voltage can play a transition role to avoid the generation of a sudden change interface, so as to improve the bonding force between the coating and the substrate.

[0014] The diffusion barrier layer is composed of metal carbide and has good high-temperature stability and chemical stability to block the outward diffusion of Ta.

[0015] The composition of the transition layer is metal carbide and Re, and in the transition layer, the content of the metal carbide decreases from inside to outside, and the content of Re increases from inside to outside, so as to improve the bonding force between the barrier layer and the thermal protection layer.

[0016] The thermal protection layer comprises Re layer, Ir layer and HfO2-Y2O3 layer from inside to outside in turn, and the arrangement of the layers in turn can prevent the diffusion of the Ta element of the substrate and the Ir element of the coating, relieve the difference in thermal expansion coefficient between Ir and the ceramic layer, and improve the bonding force of the coating.

[0017] In some preferred embodiments of the present application, the thickness of the Re layer is 400-500 nm. In some preferred embodiments of the present application, the thickness of the Ir layer is 800-1500 nm. In some preferred embodiments of the present application, the thickness of the HfO2-Y2O3 layer is 100-300 nm.

[0018] In some preferred embodiments of the present application, the metal is one or both of Re and Ta.

[0019] In some preferred embodiments of the present application, the metal carbide is one or both of HfC and TaC.

[0020] In some preferred embodiments of the present application, the thickness of the primer layer is 100-500 nm.

[0021] In some preferred embodiments of the present application, the thickness of the diffusion barrier layer is 100-500 nm.

[0022] In some preferred embodiments of the present application, the thickness of the transition layer is 50-500 nm.

[0023] The present application takes into account that conventional coatings are mainly prepared by methods such as pack cementation, thermal spraying, chemical vapor deposition and electrodeposition, but in the above preparation methods, the pack cementation and thermal spraying method are not easy to control the coating thickness and uniformity; the chemical vapor deposition method produces toxic products and causes serious corrosion of the equipment, the electrodeposition method has large coating stress and is prone to cracking, and the coating often has pinhole defects and other problems. In addition, the three main modification methods of Ir coating at present mainly include optimizing the coating structure, coating with ceramic and surface alloying, but each single modification method has limitations, the improvement of the oxidation resistance life of the Ir coating by changing the process to optimize the Ir coating structure is limited, and the latter two methods both have problems such as mismatching of the thermal expansion coefficients of Ir and ceramic layer and poor bonding force. Therefore, the present application uses the magnetron sputtering technology to prepare a coating with a composite gradient structure on the surface of a Ta substrate by the magnetron sputtering method, so as to reduce the formation of volatile oxides of iridium element, improve the bonding strength of the coating, prolong the service life of the coating and improve the overall high-temperature protection performance of the coating. The preparation method of the present application comprises the following steps:

[0024] Step 1: Pretreatment of Ta substrate

[0025] The Ta substrate is polished and cleaned to obtain a pretreated Ta substrate.

[0026] It should be noted that the present application considers that the Ta substrate surface may have impurities such as oil stains and surface defects, so the Ta substrate is polished and cleaned to remove the impurities on the surface of the Ta substrate and improve the surface roughness, so as to improve the bonding force between the Ta substrate surface and the coating.

[0027] It should be further pointed out that since the subsequent glow discharge sputtering cleaning treatment and the magnetic control sputtering process of each step are carried out in the magnetic control sputtering equipment, the pretreated Ta substrate is installed on the workpiece rotating frame in the vacuum chamber of the magnetic control sputtering equipment, so as to facilitate the subsequent deposition of the base layer, diffusion barrier layer, transition layer and thermal protection layer.

[0028] Step 2, glow discharge sputtering cleaning treatment:

[0029] The pretreated Ta substrate is subjected to glow discharge sputtering cleaning treatment to obtain a clean Ta substrate.

[0030] It should be noted that the present application considers that the pretreated Ta substrate may still have impurities such as oxides, so the pretreated Ta substrate is further subjected to glow discharge sputtering cleaning treatment to further improve the bonding force between the Ta substrate surface and the coating.

[0031] Step 3, depositing a base layer:

[0032] Under an argon atmosphere, a metal target or a metal carbide target is used as a sputtering target material, and a base layer is deposited on the surface of the clean Ta substrate by controlling the gradual decrease of the substrate bias.

[0033] It should be noted that the present application deposits a base layer with a decreasing bias gradient on the surface of the Ta substrate by gradually reducing the substrate bias, that is, the base layer formed by the present application is formed by a plurality of different base layer gradients, and such a gradient-distributed base layer can play a role in slow transition and avoiding abrupt interfaces compared with a base layer with uniform component distribution, thereby effectively solving the problems of unstable Ir coating grain boundary structure for a long time and poor interface bonding, and improving the service life of the Ir coating on the Ta substrate under working conditions.

[0034] Step 4, depositing a diffusion barrier layer:

[0035] A metal carbide target is used as a sputtering target material to deposit a diffusion barrier layer on the surface of the base layer.

[0036] It should be noted that the application deposits a layer of metal carbide layer as a diffusion barrier layer on the surface of the primer layer, so as to prevent Ta from diffusing outward by the metal carbide barrier, thereby avoiding the diffusion of Ta to the surface of the coating and causing the oxidation of Ta to oxide during service, thereby avoiding the mismatch of the thermal expansion coefficient of the coating and the substrate, so as to prolong the service life of the coating under working conditions and improve the bonding strength between the coating and the substrate.

[0037] Step 5, depositing a transition layer:

[0038] The metal carbide target and the Re target are used as co-sputtering target materials, and a transition layer with gradually reduced metal carbide composition and gradually increased Re composition is deposited on the surface of the diffusion barrier layer by gradually reducing the sputtering power of the metal carbide target and gradually increasing the sputtering power of the Re target during deposition.

[0039] It should be noted that the application further deposits a transition layer with a gradient distribution of components on the surface of the diffusion barrier layer, which not only effectively prevents the outward diffusion of the substrate Ta element, but also improves the bonding strength between the various coatings, thereby effectively improving the high-temperature protection performance and service life of the coating as a whole.

[0040] Step 6, depositing a thermal protection layer:

[0041] The Re target, Ir target and HfO2-Y2O3 target are used as sputtering targets in sequence, and the Re layer, Ir layer and HfO2-Y2O3 layer are deposited on the surface of the transition layer in sequence to form a thermal protection layer composed of the Re layer, Ir layer and HfO2-Y2O3 layer on the surface of the transition layer.

[0042] It should be noted that the application further deposits a transition layer with a gradient distribution of components on the surface of the diffusion barrier layer, which not only effectively prevents the outward diffusion of the substrate Ta element, but also improves the bonding strength between the various coatings, thereby effectively improving the high-temperature protection performance and service life of the coating as a whole.

[0043] It should be further noted that in the above steps 3-6, the application uses high-vacuum magnetron sputtering technology, which can accurately control the morphology, structure and thickness of the coating, and the co-sputtering technology can realize the composition gradient structure of the coating, thereby forming a composite gradient structure coating on the Ta-based refractory metal, and the coating is tightly bonded between the layers and the substrate, which can effectively reduce the formation of volatile oxides of iridium elements, thereby improving the high-temperature protection performance of the coating as a whole, and solving the problems of the methods of optimizing the Ir coating structure, covering the ceramic layer on the surface of the iridium coating or generating oxide ceramic layer in situ by alloying, such as the inability to maintain stable crystal boundary structure for a long time and poor interface bonding.

[0044] In some preferred embodiments of the present application, when depositing the primer layer, vacuum is first extracted to a base vacuum of ≤5*10 -4 Pa, and argon is then introduced to maintain a working pressure of 0.2 Pa to 1.5 Pa; and when sputter depositing, the sputtering power is fixed at 200 W to 300 W, and the argon flow rate is 10 sccm to 30 sccm; first, a first primer layer with a thickness of 20 nm to 100 nm is deposited under a substrate bias of -400 V to -500 V; then, the substrate bias is adjusted to -300 V to -400 V, and a second primer layer with a thickness of 20 nm to 100 nm is deposited; then, the substrate bias is adjusted to -200 V to -300 V, and a third primer layer with a thickness of 20 nm to 100 nm is deposited; finally, the substrate bias is adjusted to -100 V to -200 V, and a fourth primer layer with a thickness of 20 nm to 100 nm is deposited, so that the first primer layer, the second primer layer, the third primer layer, and the fourth primer layer together serve as the primer layer, and the effect of improving the adhesion between the coating and the substrate is further improved.

[0045] In some preferred embodiments of the present application, when depositing the diffusion barrier layer, argon is introduced, the argon flow rate is controlled to be 10 sccm to 30 sccm, the working pressure is controlled to be 0.2 Pa to 1.5 Pa, the sputtering power is 200 W to 300 W, and the substrate bias is -90 V to -120 V, so that the effect of blocking the outward diffusion of Ta is further improved.

[0046] In some preferred embodiments of the present application, during deposition of the transition layer, argon is introduced, the argon flow is controlled to be 10-30sccm, the working pressure is controlled to be 0.2-1.5Pa, the substrate bias is fixed to be -90V to -120V; a first transition layer with a thickness of 20-100nm is deposited under the conditions that the sputtering power of the metal carbide target is 200-300W and the sputtering power of the Re target is 50-100W; then a second transition layer with a thickness of 20-100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to be 100-200W and the sputtering power of the Re target is adjusted to be 100-150W; then a third transition layer with a thickness of 20-100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to be 50-100W and the sputtering power of the Re target is adjusted to be 150-200W; finally a fourth transition layer with a thickness of 20-100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to be 20-50W and the sputtering power of the Re target is adjusted to be 200-250W, so as to further effectively prevent the diffusion of the substrate Ta element outward and further improve the adhesion between the various coating layers by the first transition layer, the second transition layer, the third transition layer and the fourth transition layer which are distributed in a gradient.

[0047] In some preferred embodiments of the present application, during deposition of the thermal protection layer, argon is introduced, the argon flow is controlled to be 10-30sccm, the working pressure is controlled to be 0.2-1.5Pa, and the substrate bias is -90V to -120V; during deposition of the Re layer in the thermal protection layer, the sputtering power is 200-250W; during deposition of the Ir layer in the thermal protection layer, the sputtering power is 200-300W; and during deposition of the HfO2-Y2O3 layer in the thermal protection layer, the sputtering power is 200-300W.

[0048] In some preferred embodiments of the present application, during the glow discharge sputtering cleaning process, the vacuum is first pumped to a base vacuum degree of ≤5×10 -4 Pa, then argon is introduced, the argon flow is controlled to be 10-30sccm, the working pressure is controlled to be 0.2-1.5Pa, the substrate bias is -300V to -500V, and the cleaning time is ≥15min.

[0049] In some preferred embodiments of the present application, the pretreated Ta substrate is obtained by the following steps: sequentially polishing the Ta substrate with 400#, 800#, 1500#, 2000# and 3000# sandpaper, and then sequentially mechanically polishing with 0.5 µm, 0.25 µm and 0.05 µm diamond polishing agent until the surface is smooth and free of obvious scratches, and then sequentially ultrasonic cleaning with acetone and anhydrous ethanol for 10-15 min and drying to obtain the pretreated Ta substrate.

[0050] Compared with the prior art, the present application has the following beneficial effects:

[0051] The composite gradient structure coating of the present application comprises, from inside to outside, a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer which are sequentially stacked on the Ta substrate. The primer layer is composed of a metal or a metal carbide, and the bias voltage of the primer layer gradually decreases from inside to outside on the Ta substrate to improve the adhesion of the coating to the substrate. The diffusion barrier layer is composed of a metal carbide to block the outward diffusion of Ta. The transition layer is composed of a metal carbide and Re, and in the transition layer, the content of the metal carbide decreases from inside to outside, and the content of Re increases from inside to outside. The thermal protection layer comprises, from inside to outside, a Re layer, an Ir layer and an HfO2-Y2O3 layer, and the sequential arrangement of the layers can prevent the diffusion of the Ta element of the substrate and the Ir element of the coating, alleviate the difference in the thermal expansion coefficient between Ir and the ceramic layer, improve the adhesion of the coating, and improve the service life of the thermal protection coating and the substrate.

[0052] The present application combines various high-temperature-resistant ablative coatings in a gradient structure to overcome the defects of single-component coatings, greatly improve the corrosion resistance of the Ir coating on the surface of the Ta-based refractory alloy substrate, and reduce the formation of volatile oxides of iridium elements compared with single-component coatings, improve the adhesion of the coating, prolong the service life of the coating, and improve the overall high-temperature protection performance of the coating.

[0053] The present application uses high-vacuum magnetron sputtering technology to prepare a thermal protection coating with a composite gradient structure on a Ta-based refractory metal, which avoids the problems of the pack cementation method and the thermal spraying method, such as difficulty in controlling the thickness and uniformity of the coating, the toxic product of the chemical vapor deposition method and the serious corrosion of the equipment, the large stress and easy cracking of the coating of the electrodeposition method, and the existence of pinhole defects in the coating, and the coating is tightly combined with each layer and the substrate, which can effectively reduce the formation of volatile oxides of iridium elements, thereby improving the overall high-temperature protection performance of the coating, and solving the problems of the methods of optimizing the organizational structure of the Ir coating, covering a ceramic layer on the surface of the Ir coating or generating an oxide ceramic layer in situ through alloying, such as the inability of the grain boundary structure to remain stable for a long time and poor interface adhesion.

[0054] Compared with the traditional coating, the thermal protection coating with the composite gradient structure prepared by the magnetron sputtering technology can effectively solve the problems that the grain boundary structure of the Ir coating cannot be kept stable for a long time and the interface bonding is poor, and the service life of the Ir coating on the Ta substrate under the working condition is improved.

[0055] In the preparation process, the morphology, structure and thickness of the coating can be accurately controlled by using the magnetron sputtering technology, and the composition gradient structure of the coating can be realized by the co-sputtering technology, the diffusion of the substrate Ta element and the coating Ir element is prevented by the multilayer composite diffusion barrier layer, and the service life of the thermal protection coating and the substrate is improved.

[0056] Compared with the method of optimizing the organizational structure of the Ir coating, the preparation method of the present application is simple and easy to operate, and the structure and composition between the layers are easy to control, which can improve the service life of the coating.

[0057] Compared with the method of surface covering ceramic layer and surface alloying, the preparation method of the present application can alleviate the difference in thermal expansion coefficient between Ir and ceramic layer, and improve the bonding force of the coating. BRIEF DESCRIPTION OF DRAWINGS

[0058] Figure 1 It is a structure schematic diagram of the composite gradient structure coating of the present application.

[0059] Figure 2 It is a cross-section scanning electron microscope image of the composite gradient structure coating prepared in Example 4.

[0060] Figure 3 It is an XRD spectrum diagram of the composite gradient structure coating prepared in Example 5.

[0061] Figure 4 It is a cross-section scanning electron microscope image of the composite gradient structure coating prepared in Example 6 after high temperature annealing.

[0062] Figure 5 It is a scratch backscattering image of the composite gradient structure coating prepared in Example 6 before high temperature annealing and after high temperature annealing after scratch test; wherein, (a) is a scratch backscattering image of the composite gradient structure coating prepared in Example 6 before high temperature annealing after scratch test; (b) is a scratch backscattering image of the composite gradient structure coating prepared in Example 6 after high temperature annealing after scratch test.

[0063] Figure 6 It is a cross-section scanning electron microscope image of the coating prepared in Comparative Example 3 after high temperature annealing. DETAILED DESCRIPTION

[0064] The technical solutions in the embodiments of the present application will be described clearly and completely below.

[0065] Example 1

[0066] Referring to Figure 1 The embodiment provides a Ta-based refractory metal surface composite gradient structure coating.

[0067] The composite gradient structure coating of the embodiment comprises, from inside to outside, a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer which are sequentially stacked on a Ta substrate.

[0068] In the embodiment, the primer layer is composed of HfC.

[0069] In the embodiment, the diffusion barrier layer is composed of HfC.

[0070] In the embodiment, the transition layer is composed of HfC and Re; and in the transition layer, the content of the metal carbide decreases from inside to outside in a gradient manner, and the content of Re increases from inside to outside in a gradient manner.

[0071] In the embodiment, the thermal protection layer comprises, from inside to outside, a Re layer, an Ir layer and a HfO2-Y2O3 layer; wherein the thickness of the Re layer is 400-500 nm, the thickness of the Ir layer is 800-1500 nm, and the thickness of the HfO2-Y2O3 layer is 100-300 nm.

[0072] Embodiment 2

[0073] The embodiment provides a Ta-based refractory metal surface composite gradient structure coating.

[0074] The composite gradient structure coating of the embodiment comprises, from inside to outside, a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer which are sequentially stacked on a Ta substrate.

[0075] In the embodiment, the primer layer is composed of Re.

[0076] In the embodiment, the diffusion barrier layer is composed of HfC.

[0077] In the embodiment, the transition layer is composed of HfC and Re; and in the transition layer, the content of the metal carbide decreases from inside to outside in a gradient manner, and the content of Re increases from inside to outside in a gradient manner.

[0078] In the embodiment, the thermal protection layer comprises, from inside to outside, a Re layer, an Ir layer and a HfO2-Y2O3 layer; wherein the thickness of the Re layer is 400-500 nm, the thickness of the Ir layer is 800-1500 nm, and the thickness of the HfO2-Y2O3 layer is 100-300 nm.

[0079] Embodiment 3

[0080] The composite gradient structure coating of the embodiment comprises, from inside to outside, a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer which are sequentially stacked on the Ta base.

[0081] In the embodiment, the primer layer is composed of Ta.

[0082] In the embodiment, the diffusion barrier layer is composed of HfC.

[0083] In the embodiment, the transition layer is composed of HfC and Re; and in the transition layer, the content of the metal carbide decreases from inside to outside, and the content of Re increases from inside to outside.

[0084] In the embodiment, the thermal protection layer comprises, from inside to outside, a Re layer, an Ir layer and a HfO2-Y2O3 layer; wherein the thickness of the Re layer is 400-500 nm, the thickness of the Ir layer is 800-1500 nm, and the thickness of the HfO2-Y2O3 layer is 100-300 nm.

[0085] Embodiment 4

[0086] The embodiment provides a preparation method for preparing the composite gradient structure coating of the Ta-based refractory metal surface of Embodiment 1, and comprises the following steps.

[0087] Step 1, pretreatment of the Ta base material:

[0088] 1.1) polishing the Ta sheet with 400#, 800#, 1500#, 2000# and 3000# sandpaper in sequence.

[0089] 1.2) mechanically polishing the sample obtained in 1.1) with 0.5 μm, 0.25 μm and 0.05 μm diamond polishing agent in sequence until the surface is smooth and free of obvious scratches.

[0090] 1.3) ultrasonic cleaning the sample obtained in 1.2) with acetone and anhydrous ethanol in sequence for 15 min and drying to obtain the pretreated Ta base material.

[0091] 1.4) installing the pretreated Ta base material on the workpiece rotating stand in the vacuum chamber of the magnetron sputtering device, installing the Re target on the direct current target site, and installing the HfC target, the Ir target and the HfO2-Y2O3 target on the radio frequency target site.

[0092] Step 2, glow discharge sputtering cleaning treatment:

[0093] firstly, vacuumizing to a background vacuum degree ≤5×10 -4Pa, and then argon gas was introduced again, the argon gas flow was controlled to be 20sccm, the working pressure was controlled to be 0.5Pa, the substrate bias was -400V, and the clean Ta substrate was obtained by sputtering cleaning for 25min-30min.

[0094] Step 3, depositing a primer layer:

[0095] 3.1) The argon gas with a purity of not less than 99.9% was introduced, the argon gas flow was 20sccm, the working pressure was 0.5Pa, the sputtering power was 250W, the substrate bias was adjusted to be -400V, and a HfC layer with a thickness of 30nm was deposited as a first primer layer.

[0096] 3.2) The substrate bias was adjusted to be -300V, and a HfC layer with a thickness of 40nm was deposited as a second primer layer.

[0097] 3.3) The substrate bias was adjusted to be -200V, and a HfC layer with a thickness of 40nm was deposited as a third primer layer.

[0098] 3.4) The substrate bias was adjusted to be -100V, and a HfC layer with a thickness of 40nm was deposited as a fourth primer layer, so as to form a HfC primer layer with a thickness of 150nm and a gradient distribution on the surface of the clean Ta substrate.

[0099] Step 4, depositing a diffusion barrier layer:

[0100] The argon gas flow was controlled to be 20sccm, the working pressure was 0.5Pa, the substrate bias was -100V, the HfC target was used as the sputtering target material, the sputtering power was 250W, and a HfC layer with a thickness of 250nm was deposited on the primer layer formed in step 3.4) as a diffusion barrier layer.

[0101] Step 5, depositing a transition layer:

[0102] 5.1) The argon gas was introduced into the vacuum chamber while the HfC target and the Re target were sputtered, the argon gas flow was 20sccm, the gas pressure was controlled to be 0.5Pa, the substrate bias was fixed to be -100V, the sputtering power of the HfC target was adjusted to be 200W, the sputtering power of the Re target was 50W, a HfC-Re layer with a thickness of 40nm was deposited on the diffusion barrier layer formed in step 4 as a first transition layer.

[0103] 5.2) Under the condition that the sputtering power of the HfC target was 150W and the sputtering power of the Re target was 100W, a second transition layer with a thickness of 40nm was deposited.

[0104] 5.3) Under the condition that the sputtering power of the HfC target was 100W and the sputtering power of the Re target was 150W, a third transition layer with a thickness of 40nm was deposited.

[0105] 5.4) Adjusting the sputtering power of the HfC target to 50 W and the sputtering power of the Re target to 200 W, depositing a fourth transition layer with a thickness of 40 nm to form a transition layer with a gradient distribution and a thickness of 160 nm on the surface of the diffusion barrier layer.

[0106] Step 6, deposition of a thermal protection layer:

[0107] 6.1) Turning off the HfC target, using the Re target as the sputtering target material, controlling the argon flow rate to be 20 sccm, the working pressure to be 0.5 Pa, the substrate bias to be -100 V, and the sputtering power of the Re target to be 250 W, depositing a Re layer with a thickness of 400 nm on the transition layer formed in 5.4).

[0108] 6.2) Using the Ir target as the sputtering target material, controlling the argon flow rate to be 20 sccm, the working pressure to be 0.5 Pa, the substrate bias to be -100 V, and the sputtering power of the Ir target to be 250 W, depositing an Ir layer with a thickness of 1 μm on the Re layer formed in 6.1) as an oxidation-resistant layer.

[0109] 6.3) Using the HfO2-Y2O3 target as the sputtering target material, controlling the argon flow rate to be 20 sccm, the working pressure to be 0.5 Pa, the substrate bias to be -100 V, and the sputtering power of the HfO2-Y2O3 target to be 250 W, depositing a HfO2-Y2O3 layer with a thickness of 150 nm on the Ir layer formed in 6.2) as a ceramic protection layer.

[0110] Example 5

[0111] This example provides a preparation method for preparing the composite gradient structure coating of the Ta-based refractory metal surface of Example 2, and includes the following steps:

[0112] Step 1, pretreatment of the Ta substrate:

[0113] 1.1) Polishing the Ta sheet with 400#, 800#, 1500#, 2000#, and 3000# sandpaper in sequence.

[0114] 1.2) Mechanically polishing the sample obtained in 1.1) with 0.5 μm, 0.25 μm, and 0.05 μm diamond polishing agents in sequence until the surface is smooth and free of obvious scratches.

[0115] 1.3) Ultrasonic cleaning the sample obtained in 1.2) with acetone and anhydrous ethanol for 15 min in sequence and drying to obtain the pretreated Ta substrate.

[0116] 1.4) Install the pretreated Ta substrate on the workpiece turntable in the vacuum chamber of the magnetron sputtering device, install the Re target on the direct current target site, and install the HfC target, Ir target, and HfO2-Y2O3 target on the radio frequency target site.

[0117] Step 2, glow discharge sputtering cleaning treatment:

[0118] First, vacuumize to a background vacuum degree of ≤5×10 -4 Pa, then introduce argon gas with a purity of not less than 99.9%, control the argon gas flow to be 20 sccm, control the working gas pressure to be 0.5 Pa, control the substrate bias voltage to be -400 V, and perform glow discharge sputtering cleaning for 25 min to 30 min to obtain a clean Ta substrate.

[0119] Step 3, deposition of the primer layer:

[0120] 3.1) Introduce argon gas with a purity of not less than 99.9%, the introduced argon gas flow is 20 sccm, the working gas pressure is 0.5 Pa, the Re target is used as the sputtering target material, the sputtering power is 250 W, the substrate bias voltage is adjusted to be -400 V, and a Re layer with a thickness of 30 nm is deposited as the first primer layer.

[0121] 3.2) Adjust the substrate bias voltage to be -300 V, and deposit a Re layer with a thickness of 40 nm as the second primer layer.

[0122] 3.3) Adjust the substrate bias voltage to be -200 V, and deposit a Re layer with a thickness of 40 nm as the third primer layer.

[0123] 3.4) Adjust the substrate bias voltage to be -100 V, and deposit a Re layer with a thickness of 40 nm as the fourth primer layer, so as to form a Re primer layer with a gradient distribution and a thickness of 150 nm on the surface of the clean Ta substrate.

[0124] Step 4, deposition of the diffusion barrier layer:

[0125] Control the argon gas flow to be 20 sccm, the working gas pressure to be 0.5 Pa, and the substrate bias voltage to be -100 V, use the HfC target as the sputtering target material, and the sputtering power is 250 W, and then deposit a HfC layer with a thickness of 250 nm on the primer layer formed in step 3.4) as the diffusion barrier layer.

[0126] Step 5, deposition of the transition layer:

[0127] 5.1) The HfC target and the Re target are sputtered with argon gas flowing at 20 sccm and a pressure of 0.5 Pa, while the substrate bias is fixed at -100 V, the sputtering power of the HfC target is adjusted to 200 W, and the sputtering power of the Re target is adjusted to 50 W, to deposit a 40-nm-thick HfC-Re layer on the diffusion barrier layer formed in step 4 as a first transition layer.

[0128] 5.2) The sputtering power of the HfC target is adjusted to 150 W, and the sputtering power of the Re target is adjusted to 100 W, to deposit a 40-nm-thick second transition layer.

[0129] 5.3) The sputtering power of the HfC target is adjusted to 100 W, and the sputtering power of the Re target is adjusted to 150 W, to deposit a 40-nm-thick third transition layer.

[0130] 5.4) The sputtering power of the HfC target is adjusted to 50 W, and the sputtering power of the Re target is adjusted to 200 W, to deposit a 40-nm-thick fourth transition layer, to form a transition layer with a gradient distribution and a thickness of 160 nm on the surface of the diffusion barrier layer.

[0131] Step 6, deposition of a thermal protection layer:

[0132] 6.1) The HfC target is turned off, and the Re target is used as the sputtering target, with an argon gas flow of 20 sccm, a working pressure of 0.5 Pa, a substrate bias of -100 V, and a sputtering power of the Re target of 250 W, to deposit a 400-nm-thick Re layer on the transition layer formed in 5.4).

[0133] 6.2) The Ir target is used as the sputtering target, with an argon gas flow of 20 sccm, a working pressure of 0.5 Pa, a substrate bias of -100 V, and a sputtering power of the Ir target of 250 W, to deposit a 1-μm-thick Ir layer on the Re layer formed in 6.1) as an oxidation-resistant layer.

[0134] 6.3) The HfO2-Y2O3 target is used as the sputtering target, with an argon gas flow of 20 sccm, a working pressure of 0.5 Pa, a substrate bias of -100 V, and a sputtering power of the HfO2-Y2O3 target of 250 W, to deposit a 150-nm-thick HfO2-Y2O3 layer on the Ir layer formed in 6.2) as a ceramic protection layer.

[0135] Example 6

[0136] This example provides a preparation method for preparing the composite gradient structure coating of the Ta-based refractory metal surface of Example 3, and includes the following steps:

[0137] Step 1, pretreatment of the Ta substrate:

[0138] 1.1) Use 400#, 800#, 1500#, 2000#, 3000# sandpaper to polish the Ta sheet in turn.

[0139] 1.2) Mechanically polish the sample obtained in 1.1) with 0.5 μm, 0.25 μm and 0.05 μm diamond polishing agent in turn until the surface is smooth and free of obvious scratches.

[0140] 1.3) Ultrasonically clean the sample obtained in 1.2) with acetone and anhydrous ethanol in turn for 15 min and dry to obtain a pretreated Ta substrate.

[0141] 1.4) Install the pretreated Ta substrate on the workpiece turret in the vacuum chamber of the magnetron sputtering device, install the Ta target and Re target on the direct current target site, and install the HfC target, Ir target and HfO2-Y2O3 target on the radio frequency target site.

[0142] Step 2, glow discharge sputtering cleaning treatment:

[0143] First, vacuumize to a base vacuum degree of ≤5×10 -4 Pa, then introduce argon gas, control the argon gas flow to be 20 sccm, control the working gas pressure to be 0.5 Pa, the substrate bias voltage to be -400 V, and glow discharge sputter for 25 min to 30 min to obtain a clean Ta substrate.

[0144] Step 3, deposition of a primer layer:

[0145] 3.1) Introduce argon gas with a purity of not less than 99.9%, the introduced argon gas flow is 20 sccm, the working gas pressure is 0.5 Pa, the sputtering power is 250 W, the substrate bias voltage is adjusted to -400 V, and a Ta layer with a thickness of 30 nm is deposited as a first primer layer.

[0146] 3.2) Adjust the substrate bias voltage to -300 V, and deposit a Ta layer with a thickness of 40 nm as a second primer layer.

[0147] 3.3) Adjust the substrate bias voltage to -200 V, and deposit a Ta layer with a thickness of 40 nm as a third primer layer.

[0148] 3.4) Adjust the substrate bias voltage to -100 V, and deposit a Ta layer with a thickness of 40 nm as a fourth primer layer to form a Ta primer layer with a gradient distribution and a thickness of 150 nm on the surface of the clean Ta substrate.

[0149] Step 4, deposition of a diffusion barrier layer:

[0150] The argon flow rate was controlled to be 20 seem, the working pressure was 0.5 Pa, the substrate bias was -100 V, the HfC target was used as the sputtering target material, and the sputtering power was 250 W, so that a 250 nm-thick HfC layer was deposited on the undercoat layer formed in step 3.4) as a diffusion barrier layer.

[0151] Step 5, deposition of a transition layer:

[0152] 5.1) The argon flow rate was controlled to be 20 seem, the working pressure was 0.5 Pa, the substrate bias was -100 V, the sputtering power of the HfC target was controlled to be 200 W, and the sputtering power of the Re target was controlled to be 50 W, so that a 40 nm-thick HfC-Re layer was deposited on the diffusion barrier layer formed in step 4 as a first transition layer.

[0153] 5.2) The sputtering power of the HfC target was controlled to be 150 W, and the sputtering power of the Re target was controlled to be 100 W, so that a 40 nm-thick second transition layer was deposited.

[0154] 5.3) The sputtering power of the HfC target was controlled to be 100 W, and the sputtering power of the Re target was controlled to be 150 W, so that a 40 nm-thick third transition layer was deposited.

[0155] 5.4) The sputtering power of the HfC target was controlled to be 50 W, and the sputtering power of the Re target was controlled to be 200 W, so that a 40 nm-thick fourth transition layer was deposited, thereby forming a 160 nm-thick transition layer with a gradient distribution on the surface of the diffusion barrier layer.

[0156] Step 6, deposition of a thermal protection layer:

[0157] 6.1) The HfC target was turned off, the Re target was used as the sputtering target material, the argon flow rate was controlled to be 20 seem, the working pressure was 0.5 Pa, the substrate bias was -100 V, and the sputtering power of the Re target was controlled to be 250 W, so that a 400 nm-thick Re layer was deposited on the transition layer formed in step 5.4).

[0158] 6.2) The Ir target was used as the sputtering target material, the argon flow rate was controlled to be 20 seem, the working pressure was 0.5 Pa, the substrate bias was -100 V, and the sputtering power of the Ir target was controlled to be 250 W, so that a 1 μm-thick Ir layer was deposited on the Re layer formed in step 6.1) as an oxidation-resistant layer.

[0159] 6.3) Using HfO2-Y2O3 target as sputtering target, controlling argon flow rate to be 20 sccm, working pressure to be 0.5 Pa, substrate bias to be -100 V, and HfO2-Y2O3 target sputtering power to be 250 W, a layer of HfO2-Y2O3 with a thickness of 150 nm is deposited on the Ir layer formed in 6.2) as a ceramic protective layer.

[0160] Comparative Example 1

[0161] The only difference between the present comparative example and Example 4 is that:

[0162] In the present comparative example, the substrate bias is not adjusted when depositing the undercoat layer, i.e. the substrate bias is kept at -400 V.

[0163] Comparative Example 2

[0164] The only difference between the present comparative example and Example 4 is that:

[0165] In the present comparative example, the sputtering power of the HfC target and the Re target is not adjusted when depositing the undercoat layer, i.e. the sputtering power of the HfC target is kept at 200 W and the sputtering power of the Re target is kept at 50 W.

[0166] Comparative Example 3

[0167] The only difference between the present comparative example and Example 4 is that:

[0168] In the present comparative example, the undercoat layer is not deposited.

[0169] Experimental Part

[0170] (I) Micro-morphology test

[0171] The present application takes the composite gradient structure coating prepared in Example 4 as an example, and the cross section of the coating is tested by scanning electron microscope, and the test result is shown in Figure 2

[0172] Figure 2 The scanning electron microscope image of the cross section of the composite gradient structure coating prepared in Example 4.

[0173] As can be seen from Figure 2 , the thickness of the composite gradient structure coating prepared in Example 4 is 1.97 μm, and the coating has a clear three-layer composite gradient structure.

[0174] ​It can also be seen that in the composite gradient structure coating prepared in Embodiment 4, the innermost layer closest to the Ta substrate is the primer layer and the HfC layer, and the interface between the two is not obvious, indicating that the transition is sufficient and there is no abrupt interface. The intermediate layer is the Ir layer and the Re layer, and the interface between the two is also tightly combined without a boundary line, and the Ir / Re layer is a fine and tight columnar crystal. The outermost layer HfO2-Y2O3 is about 200 nm. The cross-section fracture of the coating is flat, the structure is dense, there is no gap, and the combination between the coating and the substrate is tight.

[0175] Based on the above, the composite gradient structure coating formed on the surface of the Ta-based refractory metal by the preparation method of the present application is tightly combined and has good bonding force with the substrate.

[0176] (II) XRD test

[0177] The surface of the composite gradient structure coating prepared in Embodiment 5 was tested by XRD, and the test results are shown in Figure 3

[0178] Figure 3 The XRD spectrum of the composite gradient structure coating prepared in Embodiment 5.

[0179] Figure 3 It can be seen that the peaks of Ir, Re, HfC coating and Ta substrate, wherein the preferred growth direction of the Ir coating is <111>, and the preferred growth direction of the Re coating is <002>, which indicates that the growth quality of each layer in the composite gradient structure coating prepared by the preparation method of the present application is good, and also verifies that the Ir / Re layer exists in the form of fine and tight columnar crystal. The peaks of HfO2 and Y2O3 are not detected, indicating that the oxide ceramic exists in the form of amorphous.

[0180] (III) Thermal protection performance test

[0181] In order to verify the thermal protection performance of the composite gradient structure coating prepared by the present application, the composite gradient structure coating prepared in Embodiment 6 was taken as an example, and the obtained coating was subjected to high temperature annealing at 1200℃ for 30min to simulate the high temperature diffusion process.

[0182] 1) Scanning electron microscope test

[0183] The cross-section of the composite gradient structure coating after annealing treatment in the above Embodiment 6 was tested by scanning electron microscope, and the test results are shown in Figure 4

[0184] Figure 4 ​​The cross-section scanning electron microscope image of the composite gradient structure coating prepared in Example 6 after high temperature annealing can be seen that the composite gradient structure coating prepared in Example 6 does not appear coating peeling and substrate damage after high temperature annealing, and the coating and the substrate are still tightly combined. This shows that the composite gradient structure coating prepared by the application has excellent thermal protection performance.

[0185] 2) Scratch test

[0186] The application also carries out scratch test on the surface of the coating of the composite gradient structure coating prepared in Example 6 before and after annealing treatment, and carries out electron backscatter diffraction test on the coating after the scratch test, and the test result is shown in Figure 5

[0187] Figure 5 The scratch backscatter images of the composite gradient structure coating prepared in Example 6 before high temperature annealing and after high temperature annealing after the scratch test; wherein, the (a) figure is the scratch backscatter image of the composite gradient structure coating prepared in Example 6 before high temperature annealing after the scratch test; the (b) figure is the scratch backscatter image of the composite gradient structure coating prepared in Example 6 after high temperature annealing after the scratch test.

[0188] By comparing the (a) figure and the (b) figure in Figure 5 , it can be seen that peeling occurs at the initial position of loading before annealing, and peeling occurs at the middle part of loading, that is, when the load is larger, after annealing, which shows that the bonding strength of the coating after annealing is improved, and there is no brittle peeling due to the difference in thermal expansion coefficient in the annealing process, and the bonding force of the coating at high temperature is still strong.

[0189] The application also carries out high temperature annealing on the coating prepared in Comparative Example 1, Comparative Example 2 and Comparative Example 3 at 1200℃ for 30min to simulate the high temperature diffusion process, and the application carries out scanning electron microscope test on the cross-section of the composite gradient structure coating after annealing treatment of the above-mentioned Comparative Example 1, Comparative Example 2 and Comparative Example 3, and the result shows that the coating prepared in Comparative Example 1-Comparative Example 3 all has obvious coating peeling and substrate damage after annealing treatment. Taking Comparative Example 3 as an example, Figure 6 The cross-section scanning electron microscope image of the coating prepared in Comparative Example 3 after high temperature annealing can be seen that the coating prepared in Comparative Example 3 has obvious breaking phenomenon after high temperature annealing. This shows that the preparation operation that the bias gradually decreases from inside to outside on the Ta substrate of the undercoat layer, and the gradient distribution of the composition of the transition layer play an important role in improving the bonding force between the coating and the substrate and the interlayer bonding force of the coating, and are the key to improve the bonding force between the coating and the substrate and the high temperature protection performance of the application.

[0190] ​The above test results prove that the base body and the coating do not appear to fall off and damage after high-temperature annealing, which indicates that the coating prepared by the preparation method of the application can effectively improve the high-temperature protection performance of the base body.

[0191] Obviously, the above-mentioned embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

Claims

1. A composite gradient structure coating for Ta-based refractory metal surfaces, characterized in that, The composite gradient structure coating is arranged on a Ta base, and the composite gradient structure coating comprises a primer layer, a diffusion barrier layer, a transition layer and a thermal protection layer arranged in sequence from inside to outside on the Ta base; The primer layer is composed of a metal or a metal carbide, and the bias voltage of the primer layer gradually decreases from inside to outside on the Ta base; The diffusion barrier layer is composed of a metal carbide; The transition layer is composed of a metal carbide and Re, and the content of the metal carbide gradually decreases and the content of Re gradually increases from inside to outside in the transition layer; The thermal protection layer comprises a Re layer, an Ir layer and an HfO2-Y2O3 layer from inside to outside; The metal is one or both of Re and Ta; The metal carbide is one or both of HfC and TaC; The composite gradient structure coating is prepared by magnetron sputtering.

2. The composite gradient structured coating of claim 1, wherein, The thickness of the Re layer is 400 nm to 500 nm; The thickness of the Ir layer is 800 nm to 1500 nm; The thickness of the HfO2-Y2O3 layer is 100 nm to 300 nm.

3. The composite gradient structured coating of claim 1, wherein, The thickness of the primer layer is 100 nm to 500 nm; The thickness of the diffusion barrier layer is 100 nm to 500 nm; The thickness of the transition layer is 50 nm to 500 nm.

4. A method for producing the composite gradient structure coating according to any one of claims 1 to 3, characterized in that The method comprises the following steps: polishing and cleaning a Ta base to obtain a pretreated Ta base; performing glow discharge sputtering cleaning treatment on the pretreated Ta base to obtain a clean Ta base; under an argon atmosphere, using a metal target or a metal carbide target as a sputtering target material, and gradually reducing the substrate bias voltage, depositing a primer layer on the surface of the clean Ta base by magnetron sputtering technology; using a metal carbide target as a sputtering target material, depositing a diffusion barrier layer on the surface of the primer layer; using a metal carbide target and a Re target as co-sputtering target materials, depositing a transition layer with a gradually decreasing content of metal carbide and a gradually increasing content of Re on the surface of the diffusion barrier layer by gradually reducing the sputtering power of the metal carbide target and gradually increasing the sputtering power of the Re target during the deposition process; sequentially using a Re target, an Ir target and an HfO2-Y2O3 target as sputtering target materials, sequentially depositing a Re layer, an Ir layer and an HfO2-Y2O3 layer on the surface of the transition layer to form a thermal protection layer composed of the Re layer, the Ir layer and the HfO2-Y2O3 layer on the surface of the transition layer.

5. The production method according to claim 4, wherein When depositing the primer layer, vacuumize to a base vacuum of ≤5×10 -4 Pa, then introduce argon gas, and maintain the working pressure at 0.2 Pa~1.5 Pa; During sputtering deposition, the fixed sputtering power is 200 W to 300 W, and the argon flow rate is 10 sccm to 30 sccm; under the condition that the substrate bias voltage is -400 V to -500 V, depositing a first primer layer with a thickness of 20 nm to 100 nm; then adjusting the substrate bias voltage to -300 V to -400 V to deposit a second primer layer with a thickness of 20 nm to 100 nm; then adjusting the substrate bias voltage to -200 V to -300 V to deposit a third primer layer with a thickness of 20 nm to 100 nm; Finally, the substrate bias is adjusted to -100V~ -200V, and a fourth primer layer with a thickness of 20nm~100nm is deposited to form the primer layer composed of the first primer layer, the second primer layer, the third primer layer and the fourth primer layer.

6. The production method according to claim 4, wherein During deposition of the transition layer, argon is introduced, the argon flow is controlled to be 10sccm~30sccm, the working pressure is controlled to be 0.2Pa~1.5Pa, and the substrate bias is fixed to be -90V~ -120V. A first transition layer with a thickness of 20nm~100nm is deposited under the conditions that the sputtering power of the metal carbide target is 200W~300W and the sputtering power of the Re target is 50W~100W; Then, a second transition layer with a thickness of 20nm~100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to 100W~200W and the sputtering power of the Re target is adjusted to 100W~150W; Then, a third transition layer with a thickness of 20nm~100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to 50W~100W and the sputtering power of the Re target is adjusted to 150W~200W; Finally, a fourth transition layer with a thickness of 20nm~100nm is deposited under the conditions that the sputtering power of the metal carbide target is adjusted to 20W~50W and the sputtering power of the Re target is adjusted to 200W~250W to form the transition layer composed of the first transition layer, the second transition layer, the third transition layer and the fourth transition layer.

7. The production method according to claim 4, wherein During deposition of the diffusion barrier layer, argon is introduced, the argon flow is controlled to be 10sccm~30sccm, the working pressure is controlled to be 0.2Pa~1.5Pa, the sputtering power is 200W~300W, and the substrate bias is -90V~ -120V.

8. The production method according to claim 4, wherein During deposition of the thermal protection layer, argon is introduced, the argon flow is controlled to be 10sccm~30sccm, the working pressure is controlled to be 0.2Pa~1.5Pa, and the substrate bias is -90V~ -120V. During deposition of the Re layer in the thermal protection layer, the sputtering power is 200W~250W. During deposition of the Ir layer in the thermal protection layer, the sputtering power is 200W~300W. During deposition of the HfO2-Y2O3 layer in the thermal protection layer, the sputtering power is 200W~300W.

9. The production method according to claim 4, wherein The glow discharge sputtering cleaning process is performed by first vacuumizing to a background vacuum degree ≤5×10 -4 Pa, then introducing argon gas, controlling the argon gas flow to be 10-30sccm, controlling the working pressure to be 0.2-1.5Pa, controlling the substrate bias to be-300--500V, and cleaning for ≥15min.

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