A TiZrAlSiN ultrahard nanolayered thin film and its preparation method
By preparing TiZrAlSiN ultrahard nanomultilayer films with a TiAl-ZrN/TiAl-ZrN/TiAlN-ZrN/ZrSiN nanomultilayer structure, the problem of hardness reduction of TiZrAlSiN coating under high-temperature oxidation environment was solved, the lubricity and wear resistance were improved, and the service life was extended.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANGHAI INST OF TECH
- Filing Date
- 2023-06-27
- Publication Date
- 2026-06-30
Smart Images
Figure CN116791030B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of physical vapor deposition surface coating technology, and in particular to a TiZrAlSiN ultrahard nano multilayer film and its preparation method. Background Technology
[0002] With the rapid development of modern manufacturing, especially the emergence of new concepts and technologies, higher demands are being placed on material performance, particularly in terms of hardness, high-temperature resistance, and wear resistance. Surface coating technology is a material surface modification technology that has developed in recent decades to meet market demands. By depositing a coating with good mechanical properties onto the material surface, the service life of cutting tools can be effectively improved, giving the tools excellent comprehensive mechanical properties, thereby significantly improving machining efficiency. Physical vapor deposition (PVD) technology is a very common material surface modification technique. Coatings prepared using PVD technology can not only effectively improve the service life of materials and reduce the amount of base material used, but also expand the performance range of previously single materials, thus broadening the application scope of materials.
[0003] In the development of coatings, ZrN films have been used in tribology, microelectronics, and decorative coatings due to their high hardness, wear resistance, and corrosion resistance. To improve their mechanical properties and thermal stability, Al, Si, and Ti are alloyed. Al, Si, and Ti are used to improve oxidation resistance by forming protective Al2O3, SiO2, and TiO2 layers on ZrN films, respectively. However, the hardness of these coatings decreases significantly when exposed to high-temperature oxidizing environments.
[0004] In the prior art, Chinese patent application publication number CN 107299314A discloses a ZrCrN / ZrAlN multilayer tool coating and its preparation method. This coating adopts a Cr / CrN-ZrCrN / ZrAlN structure and achieves a microhardness of 38.3 GPa. Chinese patent application publication number CN 112080724A discloses a method for preparing a corrosion-resistant and wear-resistant multi-component hard composite coating. This coating is a TiSiAlZrCN layer composite coating, employing a TiSiAlZrCN layer-TiSiAlZrN layer-ZrAlN layer-ZrAl layer-nitride layer-substrate structure, with a friction coefficient of 0.19.
[0005] Based on the above situation, this application focuses on in-depth research on the structure of TiSiAlZrN coatings, and further improving the lubricity, hardness and wear resistance of TiZrAlSiN coatings is the current key and difficult point. Summary of the Invention
[0006] The purpose of this invention is to provide a TiZrAlSiN ultrahard nano-multilayer thin film and its preparation method, which can improve the lubricity, hardness and wear resistance of TiZrAlSiN coating, thereby extending its service life.
[0007] To achieve the above objectives, the present invention adopts the following technical solution:
[0008] This invention provides a TiZrAlSiN ultrahard nano-multilayer thin film, characterized in that: the multilayer thin film is composed of a TiAl base layer, a ZrN / TiAl nanocomposite intermediate layer, a ZrN / TiAlN nanocomposite transition layer, and a ZrN / ZrSiN nanocomposite surface layer sequentially deposited on the surface of a substrate.
[0009] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by the present invention may also have the following feature: wherein the substrate is selected from any one of cemented carbide, high-speed steel, stainless steel and mold steel.
[0010] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by this invention may also have the following characteristics: wherein the ZrN / TiAl nanocomposite intermediate layer, the ZrN / TiAlN nanocomposite transition layer, and the ZrN / ZrSiN nanocomposite surface layer are all periodically modulated structures; the ZrN / TiAl nanocomposite intermediate layer is formed by alternating layers of ZrN and TiAl layers; the ZrN / TiAlN nanocomposite transition layer is formed by alternating layers of ZrN and TiAlN layers; and the ZrN / ZrSiN nanocomposite surface layer is formed by alternating layers of ZrN and ZrSiN layers.
[0011] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by the present invention may also have the following characteristics: wherein the thickness of the TiAl underlayer is 0.05 to 0.1 μm.
[0012] As a preferred technical solution, the thickness of the TiAl substrate is 0.1 μm.
[0013] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by the present invention may also have the following characteristics: the total thickness of the ZrN / TiAl nanocomposite intermediate layer is 0.8 to 1.2 μm, the thickness of the ZrN monolayer in the ZrN / TiAl nanocomposite intermediate layer is 40 to 60 nm, and the thickness of the TiAl monolayer in the ZrN / TiAl nanocomposite intermediate layer is 40 to 60 nm.
[0014] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by the present invention may also have the following characteristics: the total thickness of the ZrN / TiAlN nanocomposite transition layer is 0.8 to 1.2 μm, the thickness of the ZrN monolayer in the ZrN / TiAlN nanocomposite transition layer is 40 to 60 nm, and the thickness of the TiAlN monolayer in the ZrN / TiAlN nanocomposite transition layer is 40 to 60 nm.
[0015] Furthermore, the TiZrAlSiN ultrahard nanomultilayer film provided by the present invention may also have the following characteristics: the total thickness of the ZrN / ZrSiN nanocomposite surface layer is 0.8 to 1.2 μm, the thickness of the ZrN monolayer in the ZrN / ZrSiN nanocomposite surface layer is 40 to 60 nm, and the thickness of the ZrSiN monolayer in the ZrN / ZrSiN nanocomposite surface layer is 40 to 60 nm.
[0016] As a preferred technical solution, the modulation period of the ZrN / TiAl nanocomposite intermediate layer, the ZrN / TiAlN nanocomposite transition layer, and the ZrN / ZrSiN nanocomposite surface layer is 100nm, and the thickness of the ZrN / TiAl nanocomposite intermediate layer, the ZrN / TiAlN nanocomposite transition layer, and the ZrN / ZrSiN nanocomposite surface layer is 1μm.
[0017] This invention also provides a method for preparing the above-mentioned TiZrAlSiN ultrahard nanolayered thin film, characterized in that the method includes the following steps:
[0018] 1) Pre-treat the substrate to remove surface impurities and dust;
[0019] 2) Clean and etch the substrate;
[0020] 3) Preparation of TiAl substrate: By controlling the AlTi target, a TiAl substrate is prepared by deposition on the substrate surface;
[0021] 4) Preparation of ZrN / TiAl nanocomposite intermediate layer: By controlling the Zr target and AlTi target, a ZrN / TiAl nanocomposite intermediate layer is prepared on the surface of the TiAl substrate in nitrogen and nitrogen-free atmospheres.
[0022] 5) Preparation of ZrN / TiAlN nanocomposite transition layer: By controlling the Zr target and AlTi target, a ZrN / TiAlN nanocomposite transition layer is prepared on the surface of the ZrN / TiAl nanocomposite intermediate layer in a nitrogen atmosphere.
[0023] 6) Preparation of ZrN / ZrSiN nanocomposite surface layer: By controlling the Zr target and ZrSi target, a ZrN / ZrSiN nanocomposite surface layer was prepared on the surface of the ZrN / TiAlN nanocomposite transition layer in a nitrogen atmosphere.
[0024] Furthermore, the method for preparing TiZrAlSiN superhard nano-multilayer thin films provided by the present invention may also have the following features: wherein, the specific process of step 1) substrate pretreatment is as follows: polishing with a polishing machine to remove impurities from the substrate surface, ultrasonic cleaning with acetone and deionized water in sequence to remove oil and dust, and finally drying in an oven.
[0025] Furthermore, the method for preparing TiZrAlSiN superhard nanolayered films provided by this invention may also have the following characteristics: The specific process of step 2) substrate cleaning and etching is as follows: the pretreated substrate sample is loaded into a furnace with a vacuum degree of 4 × 10⁻⁶. -1 ~6×10 -1 Pa, vacuum chamber heating for 15-25 min, temperature rise to 400-500℃, argon gas flow rate of 180-220 sccm is introduced into vacuum chamber, substrate negative bias voltage of 600-700V, etching time of 15-20 min.
[0026] Furthermore, the method for preparing TiZrAlSiN ultrahard nanolayered films provided by this invention may also have the following feature: Step 3) of preparing the TiAl substrate involves a vacuum degree of 4 × 10⁻⁶. -2 ~6×10 -2 The deposition temperature was 450–550℃, the AlTi target current was 120–160A, the substrate negative bias voltage was 50–60V, and the deposition time was 5–7min.
[0027] Furthermore, the method for preparing TiZrAlSiN ultrahard nanolayered films provided by this invention may also have the following characteristics: wherein, the specific process of preparing the ZrN / TiAl nanocomposite intermediate layer in step 4) is as follows: the vacuum degree is 1-2 Pa, the deposition temperature is 450-550 °C, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber when preparing the ZrN nanolayer, the nitrogen gas is stopped when preparing the TiAl nanolayer, the AlTi target current is 120-160 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 100-140 V, and the deposition time is 50-70 min.
[0028] As a preferred technical solution, the selected target materials are alloy target AlTi target (67% Al, 33% Ti) and metal Zr target and ZrSi target (purity higher than 99.99%).
[0029] Furthermore, the method for preparing TiZrAlSiN ultrahard nanolayered films provided by this invention may also have the following characteristics: wherein, the specific process of preparing the ZrN / TiAlN nanocomposite transition layer in step 5) is as follows: the vacuum degree is 1-2 Pa, the deposition temperature is 450-550 °C, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber, the AlTi target current is 120-160 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 100-140 V, and the deposition time is 50-70 min.
[0030] Furthermore, the method for preparing TiZrAlSiN superhard nano-multilayer thin films provided by this invention may also have the following characteristics: wherein, the specific process of preparing the ZrN / ZrSiN nanocomposite surface layer in step 6) is as follows: the vacuum degree is 2-3 Pa, the deposition temperature is 450-550 °C, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber, the ZrSi target current is 100-140 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 50-70 V, and the deposition time is 50-70 min.
[0031] Compared with the prior art, the present invention has the following beneficial effects:
[0032] 1) Compared with ordinary TiZrAlSiN coatings, the nano-multilayer thin films prepared by this invention have ZrN deposited alternately in each modulation layer, which reduces the difference in expansion coefficient between films. This not only solves the problem of poor adhesion between the coating and the mold surface, but also reduces the growth of longitudinal cracks in the coating, giving the coating good toughness. This improves the surface performance of the mold and extends its service life.
[0033] 2) Compared to patent application CN 107299314A, the coating uses a Cr / CrN-ZrCrN / ZrAlN structure, achieving a microhardness of 38.3 GPa. The nano-multilayer film prepared in this invention achieves a hardness of 40.1 GPa, solving the problem of hardness reduction in coatings under high-temperature oxidation. The periodic modulation structure using TiAl as the base layer and ZrN / TiAl, ZrN / TiAlN, and ZrN / ZrSiN nano-multilayers enables the film to exhibit coherent epitaxial growth. The modulation layer experiences tensile and compressive stresses at the coherent interface, generating an alternating stress field with the modulation layer as the period in the multilayer film. This stress field significantly hinders dislocation movement and produces an age-hardening effect.
[0034] 3) Compared to patent application CN 112080724 A, the coating uses a TiSiAlZrCN layer-TiSiAlZrN layer-ZrAlN layer-ZrAl layer-nitride layer-substrate structure with a friction coefficient of 0.19. The nano-multilayer film prepared in this invention uses a TiAl-ZrN / TiAl-ZrN / TiAlN-ZrN / ZrSiN structure with a friction coefficient of 0.17, improving the film's wear resistance and extending its service life. Attached Figure Description
[0035] Figure 1 This is a schematic diagram of the structure of a TiZrAlSiN ultrahard nano multilayer film according to the present invention;
[0036] Figure 2 These are the scratch test results of the coatings in the embodiments of the present invention, Comparative Example 1, Comparative Example 2, and Comparative Example 3;
[0037] Figure 3 These are the nanoindentation test results of the coatings in the embodiments of the present invention, Comparative Example 1, Comparative Example 2, and Comparative Example 3;
[0038] Figure 4 These are the friction test results of the coatings in the embodiments of the present invention, Comparative Example 1, Comparative Example 2, and Comparative Example 3. Detailed Implementation
[0039] To make the technical means, creative features, objectives and effects of this invention easier to understand, the following embodiments, in conjunction with the accompanying drawings, will specifically illustrate the technical solution of this invention.
[0040] See Figure 1 The figure illustrates the structure of a TiZrAlSiN ultrahard nanolayered film, which includes a TiAl base layer, a ZrN / TiAl nanocomposite intermediate layer, a ZrN / TiAlN nanocomposite transition layer, and a ZrN / ZrSiN nanocomposite surface layer deposited sequentially on the substrate surface using physical vapor deposition.
[0041] The preparation process of TiZrAlSiN ultrahard nanolayered thin films is as follows:
[0042] The specific process for preparing the TiAl substrate is as follows: the vacuum degree is 4×10 -2 ~6×10 -2 The deposition temperature was 450–550℃, the AlTi target current was 120–160A, the substrate negative bias voltage was 50–60V, and the deposition time was 5–7min.
[0043] The specific process for preparing the ZrN / TiAl nanocomposite intermediate layer is as follows: the vacuum degree is 1-2 Pa, the deposition temperature is 450-550℃, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber when preparing the ZrN nanolayer, the nitrogen gas is stopped when preparing the TiAl nanolayer, the AlTi target current is 120-160 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 100-140 V, and the deposition time is 50-70 min.
[0044] The specific process for preparing the ZrN / TiAlN nanocomposite transition layer is as follows: the vacuum degree is 1-2 Pa, the deposition temperature is 450-550℃, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber, the AlTi target current is 120-160 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 100-140 V, and the deposition time is 50-70 min.
[0045] The specific process for preparing the ZrN / ZrSiN nanocomposite surface layer is as follows: the vacuum degree is 2-3 Pa, the deposition temperature is 450-550℃, nitrogen gas with a flow rate of 90-100 sccm is introduced into the vacuum chamber, the ZrSi target current is 100-140 A, the Zr target current is 90-100 A, the substrate negative bias voltage is 50-70 V, and the deposition time is 50-70 min.
[0046] The following are detailed implementation examples to further illustrate the technical solution of the present invention.
[0047] <Example>
[0048] This embodiment prepares a TiZrAlSiN ultrahard nanolayered thin film. The film structure is a TiAl-ZrN / TiAl-ZrN / TiAlN-ZrN / ZrSiN multilayered nanostructure. The specific preparation process is as follows:
[0049] 1) Matrix pretreatment:
[0050] The substrate used in this embodiment is stainless steel.
[0051] The substrate surface is polished with a polishing machine to remove impurities. Then, it is ultrasonically cleaned with acetone and deionized water to remove oil and dust. Finally, it is dried in an oven.
[0052] 2) Substrate cleaning and etching:
[0053] The pretreated matrix sample was loaded into the furnace, and the vacuum degree was 5×10⁻⁶. -1 Pa, vacuum chamber heated for 20 min, temperature increased to 450℃, argon gas with a flow rate of 200 sccm was introduced into the vacuum chamber, substrate negative bias voltage 600V, etching time 20 min.
[0054] 3) Preparation of TiAl substrate:
[0055] Vacuum degree is 5×10 -2 The deposition conditions were: Pa, deposition temperature 500℃, AlTi target current 140A, substrate negative bias voltage 60V, and deposition time 6min.
[0056] 4) Preparation of ZrN / TiAl nanocomposite intermediate layer:
[0057] The vacuum level was 1.8 Pa, the deposition temperature was 500 °C, nitrogen gas with a flow rate of 100 sccm was introduced into the vacuum chamber when preparing the ZrN nanolayer, and the nitrogen gas was stopped when preparing the TiAl nanolayer. The AlTi target current was 140 A, the Zr target current was 90 A, the substrate negative bias voltage was 120 V, and the deposition time was 60 min.
[0058] 5) Preparation of ZrN / TiAlN nanocomposite transition layer:
[0059] The vacuum level was 1.8 Pa, the deposition temperature was 500 °C, nitrogen gas was introduced into the vacuum chamber at a flow rate of 100 sccm, the AlTi target current was 140 A, the Zr target current was 90 A, the substrate negative bias voltage was 120 V, and the deposition time was 60 min.
[0060] 6) Preparation of ZrN / ZrSiN nanocomposite surface layer:
[0061] The vacuum level was 2.8 Pa, the deposition temperature was 500 °C, nitrogen gas was introduced into the vacuum chamber at a flow rate of 100 sccm, the ZrSi target current was 120 A, the Zr target current was 90 A, the substrate negative bias voltage was 60 V, and the deposition time was 60 min.
[0062] <Comparative Example 1>
[0063] Comparative Example 1 prepared a TiAl-ZrN / TiAlN-ZrN / ZrSiN nanolayered thin film, which, compared with the examples, does not contain a ZrN / TiAl nanocomposite intermediate layer. The specific preparation process is as follows:
[0064] 1) Matrix pretreatment: The matrix pretreatment steps are the same as those in the embodiment.
[0065] 2) Substrate cleaning and etching: The substrate cleaning and etching steps are the same as those in the embodiment.
[0066] 3) Preparation of TiAl substrate: The same steps as in the example of TiAl substrate preparation.
[0067] 4) Preparation of ZrN / TiAlN nanocomposite transition layer: The steps are the same as those for the ZrN / TiAlN nanocomposite transition layer in the example.
[0068] 5) Preparation of ZrN / ZrSiN nanocomposite surface layer: The steps are the same as those for the ZrN / ZrSiN nanocomposite surface layer in the example.
[0069] <Comparative Example 2>
[0070] Comparative Example 2 prepared a TiAl-ZrN / TiAl-ZrN / ZrSiN nanolayered thin film, which, compared with the examples, does not contain a ZrN / TiAlN nanocomposite transition layer. The specific preparation process is as follows:
[0071] 1) Matrix pretreatment: The matrix pretreatment steps are the same as those in the embodiment.
[0072] 2) Substrate cleaning and etching: The substrate cleaning and etching steps are the same as those in the embodiment.
[0073] 3) Preparation of TiAl substrate: The same steps as in the example of TiAl substrate preparation.
[0074] 4) Preparation of ZrN / TiAl nanocomposite intermediate layer: The steps are the same as those for the ZrN / TiAl nanocomposite intermediate layer in the example.
[0075] 5) Preparation of ZrN / ZrSiN nanocomposite surface layer: The steps are the same as those for the ZrN / ZrSiN nanocomposite surface layer in the example.
[0076] <Comparative Example 3>
[0077] Comparative Example 3 prepared a TiAl-ZrN / TiAl-ZrN / TiAlN nanolayered thin film, which, compared with the examples, does not contain a ZrN / ZrSiN nanocomposite surface layer. The specific preparation process is as follows:
[0078] 1) Matrix pretreatment: The matrix pretreatment steps are the same as those in the embodiment.
[0079] 2) Substrate cleaning and etching: The substrate cleaning and etching steps are the same as those in the embodiment.
[0080] 3) Preparation of TiAl substrate: The same steps as in the example of TiAl substrate preparation.
[0081] 4) Preparation of ZrN / TiAl nanocomposite intermediate layer: The steps are the same as those for the ZrN / TiAl nanocomposite intermediate layer in the example.
[0082] 5) Preparation of ZrN / TiAlN nanocomposite transition layer: The steps are the same as those for the ZrN / TiAlN nanocomposite transition layer in the example.
[0083] <Scratch Test>
[0084] Scratch tests were performed on the samples from Examples 1, 2, and 3. The experimental parameters were as follows: At the initial sliding position of the scriber, the load was increased from 0 N to 1 N and held for 10 seconds. During the scratching process, the load was increased from 1 N to 100 N, the speed was 20 N / min, and the sliding displacement was 4 mm. This process was repeated three times. The scratch test results are as follows. Figure 2 As shown. From Figure 2 As can be seen from the above, the TiZrAlSiN ultrahard nanolayered film sample of the present invention exhibits better bonding strength.
[0085] <Nanoindentation Test>
[0086] Nanoindentation tests were performed on the samples from Examples 1, 2, and 3. According to ISO-14577, to avoid the influence of the substrate on the coating hardness test, the indentation depth was less than 1 / 10 of the coating thickness. The experimental parameters were as follows: a Berkovich diamond indenter nanohardness tester, a constant load of 10 mN, a loading time of 30 s, a holding time of 5 s, and an unloading time of 30 s. Ten repeated experiments were performed on different parts of the same sample, and the average value was taken. The nanoindentation test results are as follows: Figure 3 As shown. From Figure 3 As can be seen from the above, the TiZrAlSiN ultrahard nanolayered film sample of the present invention has higher hardness.
[0087] High-Temperature Friction Test
[0088] The samples from Examples 1, 2, and 3 were subjected to room temperature friction tests. The experimental parameters were as follows: room temperature; WC-Co balls (diameter Φ = 6.35 mm) as the friction pair; dry friction; normal load of 5 N; frequency of 5 Hz; friction time of 10 min; friction radius of 4 mm; and three cycles of friction were performed, with the average value taken. The results of the room temperature friction tests are shown below. Figure 4 As shown in the figure, the TiZrAlSiN ultrahard nanolayered film sample of this invention has good friction properties.
[0089] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above-described embodiments. Even if various other modifications are made to the present invention, if these modifications fall within the scope of the claims of the present invention and their equivalents, they shall still fall within the protection scope of the present invention.
Claims
1. A TiZrAlSiN ultrahard nanolayered thin film, characterized in that: The multilayer film consists of a TiAl base layer, a ZrN / TiAl nanocomposite intermediate layer, a ZrN / TiAlN nanocomposite transition layer, and a ZrN / ZrSiN nanocomposite surface layer sequentially deposited on the surface of the substrate. The ZrN / TiAl nanocomposite intermediate layer, the ZrN / TiAlN nanocomposite transition layer, and the ZrN / ZrSiN nanocomposite surface layer are all periodically modulated structures. The ZrN / TiAl nanocomposite intermediate layer is composed of alternating ZrN layers and TiAl layers; The ZrN / TiAlN nanocomposite transition layer is composed of alternating ZrN and TiAlN layers; The ZrN / ZrSiN nanocomposite surface layer is composed of alternating ZrN and ZrSiN layers.
2. The TiZrAlSiN ultrahard nanolayered thin film as described in claim 1, characterized in that: The thickness of the TiAl substrate is 0.05~0.1μm; The total thickness of the ZrN / TiAl nanocomposite intermediate layer is 0.8~1.2μm, the thickness of the ZrN monolayer in the ZrN / TiAl nanocomposite intermediate layer is 40~60nm, and the thickness of the TiAl monolayer in the ZrN / TiAl nanocomposite intermediate layer is 40~60nm. The total thickness of the ZrN / TiAlN nanocomposite transition layer is 0.8~1.2μm, the thickness of the ZrN monolayer in the ZrN / TiAlN nanocomposite transition layer is 40~60nm, and the thickness of the TiAlN monolayer in the ZrN / TiAlN nanocomposite transition layer is 40~60nm. The total thickness of the ZrN / ZrSiN nanocomposite surface layer is 0.8~1.2μm, the thickness of the ZrN monolayer in the ZrN / ZrSiN nanocomposite surface layer is 40~60nm, and the thickness of the ZrSiN monolayer in the ZrN / ZrSiN nanocomposite surface layer is 40~60nm.
3. The method for preparing a TiZrAlSiN ultrahard nanolayered thin film as described in claim 1 or 2, characterized in that, The method includes the following steps: 1) Pre-treat the substrate to remove surface impurities and dust; 2) Clean and etch the substrate; 3) Preparation of TiAl substrate: By controlling the AlTi target, a TiAl substrate is prepared by deposition on the substrate surface; 4) Preparation of ZrN / TiAl nanocomposite intermediate layer: By controlling the Zr target and AlTi target, a ZrN / TiAl nanocomposite intermediate layer is prepared on the surface of the TiAl substrate in nitrogen and nitrogen-free atmospheres. 5) Preparation of ZrN / TiAlN nanocomposite transition layer: By controlling the Zr target and AlTi target, a ZrN / TiAlN nanocomposite transition layer is prepared on the surface of the ZrN / TiAl nanocomposite intermediate layer in a nitrogen atmosphere. 6) Preparation of ZrN / ZrSiN nanocomposite surface layer: By controlling the Zr target and ZrSi target, a ZrN / ZrSiN nanocomposite surface layer was prepared on the surface of the ZrN / TiAlN nanocomposite transition layer in a nitrogen atmosphere.
4. The preparation method according to claim 3, characterized in that: in, Step 1) Specific process of substrate pretreatment: Use a polishing machine to grind and polish to remove impurities from the substrate surface, then use acetone and deionized water in sequence for ultrasonic cleaning to remove oil and dust, and finally dry in an oven.
5. The preparation method according to claim 3, characterized in that: in, Step 2) The specific process of cleaning and etching the substrate is as follows: the pretreated substrate sample is loaded into the furnace, the vacuum degree is 4x10 -1 ~ 6x10 -1 Pa, the vacuum chamber is heated for 15-25 min, the temperature is raised to 400-500 ℃, argon gas with a flow rate of 180-220 sccm is introduced into the vacuum chamber, the substrate negative bias is 600-700 V, and the etching time is 15-20 min.
6. The preparation method according to claim 3, characterized in that: in, Step 3) The specific process for preparing the TiAl substrate is as follows: the vacuum degree is 4×10 -2 ~ 6×10 -2 The deposition temperature was 450~550 ℃, the AlTi target current was 120~160A, the substrate negative bias voltage was 50~60V, and the deposition time was 5~7min.
7. The preparation method according to claim 3, characterized in that: in, Step 4) The specific process for preparing the ZrN / TiAl nanocomposite intermediate layer is as follows: the vacuum degree is 1~2 Pa, the deposition temperature is 450~550 ℃, nitrogen gas with a flow rate of 90~100 sccm is introduced into the vacuum chamber when preparing the ZrN nanolayer, and the nitrogen gas is stopped when preparing the TiAl nanolayer. The AlTi target current is 120~160A, the Zr target current is 90~100A, the substrate negative bias voltage is 100~140V, and the deposition time is 50~70min.
8. The preparation method according to claim 3, characterized in that: in, Step 5) The specific process for preparing the ZrN / TiAlN nanocomposite transition layer is as follows: the vacuum degree is 1~2 Pa, the deposition temperature is 450~550 ℃, nitrogen gas with a flow rate of 90~100 sccm is introduced into the vacuum chamber, the AlTi target current is 120~160A, the Zr target current is 90~100A, the substrate negative bias voltage is 100~140V, and the deposition time is 50~70min.
9. The preparation method according to claim 3, characterized in that: in, Step 6) The specific process for preparing the ZrN / ZrSiN nanocomposite surface layer is as follows: the vacuum degree is 2~3 Pa, the deposition temperature is 450~550 ℃, nitrogen gas with a flow rate of 90~100 sccm is introduced into the vacuum chamber, the ZrSi target current is 100~140A, the Zr target current is 90~100A, the substrate negative bias voltage is 50~70V, and the deposition time is 50~70min.