Metal / toughened high-entropy nitride ceramic coating and method of making same

Abstract

This invention belongs to the field of coating technology, specifically relating to a metal / toughened high-entropy nitride ceramic coating and its preparation method. The coating consists of a Ti underlayer and a Ti / CrTiAlSiYN functional layer, arranged sequentially from the inside out on the substrate surface. The Ti / CrTiAlSiYN functional layer is a multilayer structure composed of alternating layers of Ti nanolayers and CrTiAlSiYN nanolayers. The nano-multilayer Ti / CrTiAlSiYN composite coating is prepared using magnetron sputtering combined with multi-arc ion plating technology. Preferential deposition of Ti on the substrate surface effectively improves the adhesion between the substrate and the film layer, further enhancing the Ti / CrTiAlSiYN coating's ability to suppress the erosion of the metal alloy substrate by high-temperature particles, thereby improving the service life of metal materials such as compressor blades.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to a metal / toughened high-entropy nitride ceramic coating and its preparation method. Background Technology

[0002] In power equipment such as aero engines and gas turbines, compressor blades, as core rotating components, operate in extremely harsh environments. Blades must withstand long-term high temperatures and high-speed airflow, while also facing erosion and wear from hard particles in the air (such as sand, dust, and metal oxide debris). This type of surface damage caused by high-speed solid particle impact (SPE) is one of the main causes of compressor blade failure.

[0003] Iron-based heat-resistant steels and nickel-based superalloys are widely used in compressor blade manufacturing due to their excellent high-temperature strength, creep resistance, good toughness, and machinability. However, as equipment develops towards higher parameters and longer service life, the SPE resistance of blade materials faces severe challenges. The surface hardness and wear resistance of iron-based heat-resistant steels and nickel-based superalloys are insufficient to meet the requirements of extreme operating conditions. Specifically, under high-speed particle impact, the blade surface is prone to scratches, spalling, and even material loss, which not only leads to a decrease in aerodynamic performance but also causes stress concentration, accelerates the initiation and propagation of fatigue cracks, ultimately shortens the service life of the blade, and increases equipment maintenance costs and safety risks.

[0004] Surface coating technology has become a key technological breakthrough for improving the reliability of compressor blades, enhancing their performance. In addition to high hardness and strong erosion resistance, anti-SPE coatings must also meet stringent process compatibility requirements: the coating must form a good metallurgical bond with substrate materials such as iron-based heat-resistant steel and nickel-based high-temperature alloys to avoid internal stress during service caused by mismatched coefficients of thermal expansion; simultaneously, the coating thickness and microstructure must be controlled to ensure that the aerodynamic shape and overall mechanical properties of the blade are not affected. However, traditional coating preparation methods struggle to balance coating adhesion, density, and compositional uniformity, limiting their application in the field of SPE protection for compressor blades.

[0005] In addition, regarding coating composition, existing anti-SPE coating technologies, while single-metal coatings (such as Ti coatings) can improve surface properties to some extent, suffer from insufficient hardness and poor high-temperature erosion stability. Traditional single-component ceramic coatings, on the other hand, are brittle and have weak adhesion to the substrate, making them prone to cracking and detachment under repeated impact loads, thus failing to provide long-term protection. High-entropy alloy coatings, with their excellent mechanical properties (high hardness, high toughness) and environmental stability resulting from the synergistic effect of multiple components, offer a new approach to solving this problem. However, improving their bonding strength with the substrate remains a key focus and challenge in current research. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a metal / toughened high-entropy nitride ceramic coating and its preparation method. Based on a multilayer structure design, this invention improves the bonding performance between the substrate and functional layers by using a Ti-based underlayer. Utilizing the staggered stacking structure of Ti nanolayers and CrTiAlSiYN high-entropy alloy nanolayers, it achieves synergistic optimization of hardness and toughness. Combining the process advantages of magnetron sputtering and multi-arc ion plating technologies, a coating with high adhesion, high hardness, and excellent SPE resistance is prepared. This has significant engineering application value for solving the erosion and wear problem of compressor blades and extending equipment service life, and it also aligns with the trend of advanced coating technology towards "structural-functional integration" and "multi-process composite."

[0007] This invention is specifically achieved through the following technical solutions: The first objective of this invention is to provide a metal / toughened high-entropy nitride ceramic coating, wherein the coating comprises, from the inside to the outside, a Ti underlayer and a Ti / CrTiAlSiYN functional layer from the substrate surface.

[0008] The Ti / CrTiAlSiYN functional layer is a multilayer structure composed of Ti nanolayers and CrTiAlSiYN nanolayers stacked alternately. The outermost layer of the multilayer structure is the CrTiAlSiYN nanolayer, in which the structure of the CrTiAlSiYN nanolayer is an amorphous nanocrystalline structure and the structure of the Ti nanolayer is columnar crystal. The total thickness of the metal / toughened high-entropy nitride ceramic coating is not less than 15 μm.

[0009] It should be noted that in the Ti / CrTiAlSiYN functional layer, either the Ti nanolayer or the CrTiAlSiYN nanolayer is deposited first on the Ti substrate. In other words, either the Ti nanolayer or the CrTiAlSiYN nanolayer can be deposited first on the Ti substrate. For process considerations, the outermost layer is the CrTiAlSiYN layer. Given the possibility of forming multiple complete cycles, the Ti nanolayer is preferentially deposited on the Ti substrate.

[0010] The nanocomposite coating provided by this invention first deposits a pure Ti coating on the substrate surface before the functional layer is prepared, thereby improving the problem of coating peeling and cracking caused by lattice mismatch between the coating and the substrate when the coating is directly deposited on the substrate. The Ti / CrTiAlSiYN nanomultilayer composite film of this invention improves upon the columnar crystal defects of single-layer coatings. Compared to the single-layer structure coatings of existing technologies, the nanomultilayer structure formed by the stacking of nano-scale Ti and CrTiAlSiYN sublayers of this invention helps to hinder the propagation of microcracks within the coating, improving the coating's wear resistance. Therefore, the coating of this invention is more compact and dense, has better mechanical properties, and is more effective in preventing surface damage caused by high-speed solid particle impacts.

[0011] Preferably, the thickness of the Ti substrate is 100nm~300nm.

[0012] The Ti nanolayer was prepared by magnetron sputtering, and the thickness of the Ti nanolayer was 500 nm.

[0013] The CrTiAlSiYN nanolayers were prepared using multi-arc ion plating. The thickness ratio of the CrTiAlSiYN nanolayers to the Ti nanolayers was 4:1 to 4, for example, 2:1 (CrTiAlSiYN nanolayer thickness 1 μm), 4:1 (CrTiAlSiYN nanolayer thickness 2 μm), and 1:1 (CrTiAlSiYN nanolayer thickness 0.5 μm). In the same sample, a constant thickness for the CrTiAlSiYN nanolayers was preferred.

[0014] The second objective of this invention is to provide a method for preparing a metal / toughened high-entropy nitride ceramic coating. This method involves first depositing a Ti coating on a substrate as an underlayer; then depositing a Ti / CrTiAlSiYN functional layer on the Ti underlayer, comprising the following steps: The substrate is ground, polished, and cleaned to obtain the pretreated sample; The surface of the pretreated sample was etched by an ion source. Ar gas was introduced into a high vacuum environment, and the ion source was used to bombard the sample surface under high bias voltage to remove surface impurities and adsorption, thus obtaining the etched sample. Multi-arc ion plating was used to deposit Ti on the etched sample surface to obtain a Ti underlayer; during the deposition of the Ti underlayer, the substrate bias value was set sequentially from high to low. Depositing a Ti / CrTiAlSiYN functional layer on a Ti substrate: When depositing Ti nanolayers, magnetron sputtering is used to deposit Ti magnetron targets under an inert atmosphere to obtain Ti nanolayers; When depositing CrTiAlSiYN nanolayers, multi-arc ion plating is used to deposit CrTiAlSiY multi-arc targets under a nitrogen atmosphere to obtain CrTiAlSiYN nanolayers. Ti nanolayers and CrTiAlSiYN nanolayers are deposited alternately in cycles to the desired thickness (it should be noted that the cycle period is determined by the required thickness of the film and is not a fixed value) to obtain a metal / toughened high-entropy nitride ceramic coating.

[0015] Preferably, a Ti nanolayer is first deposited on the surface of the Ti substrate, and then a CrTiAlSiYN nanolayer is deposited on the Ti nanolayer.

[0016] Specifically, it includes the following steps: S1. Pretreatment: Grinding, polishing, and cleaning the substrate; S2. Ion source etching: Ar gas is introduced into a high vacuum environment, and the sample surface under high bias voltage is bombarded by an ion source to remove surface impurities and adsorption. S3, Ti underlayer deposition: turn on the multi-arc target of metallic Ti, and sequentially deposit Ti layers on the sample surface using substrate bias values ​​from high to low to obtain the Ti underlayer. S4, Functional layer deposition: Open the Ti magnetron target, introduce Ar gas, and rotate the substrate after the Ti bottom layer deposition obtained in S3 in the furnace to obtain the Ti nanolayer. S5, functional layer deposition: turn off the Ti target, turn on the CrTiAlSiY multi-arc target, introduce N2 gas, and rotate the substrate after the Ti nanolayer deposition obtained in S4 in the furnace to obtain the CrTiAlSiYN nanolayer.

[0017] S6, Functional layer cycle, the corresponding modulation cycle is determined according to the film thickness requirements, that is, the number of cycles of S4 and S5.

[0018] Preferably, this invention innovatively uses a rotation method for coating preparation. When depositing Ti nanolayers and CrTiAlSiYN nanolayers, the CrTiAlSiY multi-arc target and the Ti magnetron target are arranged in opposite directions. While opening the Ti magnetron target or the CrTiAlSiY multi-arc target, the sample rack rotates uniformly within the furnace, thereby preparing the film and effectively controlling the film modulation ratio. This invention leverages the advantages of magnetron sputtering for depositing dense metal coatings without large particles, and the high speed and efficiency of arc ion plating; therefore, this invention is simple to operate, has a fast deposition rate, and is beneficial for large-scale mass production in industry.

[0019] Preferably, when preparing the Ti substrate, the target material used is a pure Ti multi-arc target, the working gas flow rate is 170sccm~190sccm, the vacuum degree is 0.6Pa~0.8Pa, the substrate bias voltage is 100V~600V, the Ti multi-arc target current is 90A~110A, and the deposition temperature is 380℃~420℃. Specifically, the substrate bias voltage can be set to 500V / 300V / 200V respectively, and the deposition time is 5min~15min.

[0020] Preferably, when preparing Ti nanolayers and CrTiAlSiYN nanolayers, the target materials used are a pure Ti magnetron target and a CrTiAlSiY multi-arc target, respectively. The working gas flow rate is 400 sccm to 1500 sccm, the vacuum degree is 1.5 Pa to 5 Pa, the substrate bias voltage is 90 V to 120 V, the Ti magnetron target current is 8 A to 15 A, the CrTiAlSiY multi-arc target current is 100 A to 120 A, the total deposition time is 150 min to 200 min, the deposition temperature is 380 °C to 420 °C, and the turntable speed is 8 r / min to 12 r / min.

[0021] Preferably, during ion source etching, Ar gas is introduced in a high vacuum environment with a vacuum degree of 0.6 Pa to 0.8 Pa, a temperature of 400 °C, a substrate bias voltage of 550 V to 650 V, and an etching time of 15 min to 25 min, in order to clean and activate the substrate surface.

[0022] Preferably, the matrix is ​​iron-based heat-resistant steel and nickel-based high-temperature alloy.

[0023] Preferably, the wet sandpaper used for grinding has a mesh size of 400#, 800#, 1200#, 1500#, or 2000#; the corundum powder used for polishing has a particle size of 0.8μm to 1.2μm, and the sample surface is bombarded with a pressure of 0.3 MPa to 0.6 MPa.

[0024] Preferably, the solvents used for cleaning the substrate are ethanol and acetone, and ultrasonic cleaning is performed for 5 to 15 minutes.

[0025] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a metal / toughened high-entropy nitride ceramic coating based on a multilayer structure design. From the substrate surface, the coating consists of: a Ti underlayer and a Ti / CrTiAlSiYN functional layer. The Ti / CrTiAlSiYN functional layer is a multilayer structure formed by sequentially and alternately stacking Ti nanolayers and CrTiAlSiYN nanolayers, with a total coating thickness of not less than 15 μm. Depositing the Ti underlayer first on the substrate surface before depositing the functional layer yields better results. The Ti / CrTiAlSiYN functional layer of this invention is a nano-multilayer composite film, which improves upon the columnar crystal defects of single-layer coatings. Compared to existing single-layer coatings, the nano-multilayer structure formed by the stacked Ti nanolayers and CrTiAlSiYN nanolayers of this invention helps to hinder the propagation of microcracks within the coating, improving its wear resistance. Therefore, the coating of this invention is more compact and dense, has better mechanical properties, and is more effective in preventing surface damage caused by high-speed solid particle impacts. The nanocomposite coating provided by this invention first deposits a pure Ti coating on the surface of the substrate before the functional layer is prepared, and then deposits the functional layer. This improves the problem of coating peeling and cracking caused by lattice mismatch between the coating and the substrate when the coating is directly deposited on the substrate.

[0026] This invention innovatively uses a rotation method for coating preparation, so that the multi-arc target CrTiAlSiY and the magnetron target Ti are distributed in opposite directions. While opening the Ti target and the CrTiAlSiY target, the sample rack is rotated at a constant speed in the furnace to prepare the film layer, which effectively achieves the control of the film layer modulation ratio.

[0027] This invention leverages the advantages of magnetron sputtering for depositing dense, particle-free metal coatings and the high speed and efficiency of arc ion plating; therefore, this invention is simple to operate, has a fast deposition rate, and is beneficial for large-scale mass production in industry. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the metal / toughened high-entropy nitride ceramic coating prepared in Example 1, wherein the CrTiAlSiYN layer is an amorphous nanocrystalline structure and the Ti metal layer is a columnar crystalline layer.

[0029] Figure 2 These are actual photos of the Ti / CrTiAlSiYN composite coating prepared according to the method in Example 1.

[0030] Figure 3 This is a schematic diagram of the Ti / CrTiAlSiYN composite coating prepared by the rotation method of this invention.

[0031] Figure 4The figures show the test results of the coating's crack resistance, where (a) is the coating prepared in Comparative Example 1, and (b) is the Ti / CrTiAlSiYN composite coating prepared in Example 1. Detailed Implementation

[0032] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below with reference to specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention. Unless otherwise specified, the experimental methods and detection methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials described are commercially available.

[0033] This invention employs a rotational method to prepare Ti / CrTiAlSiYN functional layers. A multi-arc target and a magnetron target are arranged facing each other. During deposition, the alternating growth of the coating is achieved by rotating the sample holder within the furnace. A schematic diagram of the rotational method mechanism of this invention is shown below. Figure 3 As shown, the CrTiAlSiY multi-arc target 2 and the Ti magnetron target 1 are arranged opposite each other. The sample is placed on the sample holder 3 and the sample holder 3 is rotated. N2 gas or Ar gas is introduced at the gas inlet 6. Vacuum is drawn using the vacuum pump 4 and a negative bias voltage 5 is applied. When depositing the Ti nanolayer, the Ti magnetron target 1 is turned on, Ar gas is introduced, the sample holder 3 is rotated, and the Ti nanolayer is obtained on the sample surface. When depositing the CrTiAlSiYN nanolayer, the Ti magnetron target 1 is turned off, the CrTiAlSiY multi-arc target 2 is turned on, N2 gas is introduced, the sample holder 3 is rotated, and the CrTiAlSiYN nanolayer is obtained on the sample surface.

[0034] The content of this invention will be described in detail below.

[0035] Example 1 A metal / toughened high-entropy nitride ceramic coating, such as Figure 1 As shown, the coating consists of a Ti underlayer 20 and a Ti / CrTiAlSiYN functional layer, arranged sequentially from the inside to the outside of the substrate 10 surface.

[0036] The Ti / CrTiAlSiYN functional layer is a multilayer structure composed of Ti nanolayer 30 and CrTiAlSiYN nanolayer 40 stacked alternately. First, Ti nanolayer 30 is deposited on Ti base layer 20. The outermost layer of the multilayer structure is CrTiAlSiYN nanolayer 40, in which the structure of CrTiAlSiYN nanolayer 40 is amorphous nanocrystalline structure, and the structure of Ti nanolayer 30 is columnar crystal.

[0037] The preparation method of the above-mentioned metal / toughened high-entropy nitride ceramic coating includes the following steps: S1. Pretreatment: Grinding, polishing, and cleaning the substrate; The substrate was selected from nickel-based high-temperature alloy N80A. The wet sandpaper used for grinding the substrate had grits of 400#, 800#, 1200#, 1500#, and 2000#. The corundum powder used for polishing had a particle size of 1μm. The sample surface was bombarded with a pressure of 0.2 MPa. The solvents used for ultrasonic cleaning of the substrate were ethanol and acetone, and the cleaning time was 10 min for each.

[0038] S2. Ion source etching: Ar gas is introduced into a high vacuum environment, and the sample surface under high bias voltage is bombarded by an ion source to remove surface impurities and adsorption.

[0039] The ion source etching process involves introducing Ar gas into a high vacuum environment with a vacuum level of 0.7 Pa, a temperature of 400 °C, an ion source voltage of 500 V, a substrate bias voltage of 600 V, and an etching time of 20 min, in order to clean and activate the substrate surface.

[0040] S3. Deposit the Ti layer. Turn on the Ti target and deposit Ti layers on the sample surface sequentially using substrate bias values ​​from high to low to obtain the Ti underlayer. The thickness of the Ti underlayer is 200 nm.

[0041] The multi-arc target used for the underlayer deposition was a pure Ti target, with a Ti multi-arc target current of 100A. The substrate bias voltage was set from high to low as 500V / 300V / 200V, and the deposition time was 10min for each. Ar ion etching and underlayer deposition were performed on the substrate surface. The Ar gas flow rate was 180sccm, the vacuum degree was 0.7 Pa, the operating temperature was 400℃, and the rotary table speed was 10r / min.

[0042] S4. Functional layer deposition: Open the Ti magnetron target and introduce Ar gas. The substrate after the Ti underlayer deposition obtained in S3 is rotated in the furnace to obtain a Ti nanolayer; the thickness of the Ti nanolayer is 500 nm.

[0043] The magnetron target used for functional layer deposition was a pure Ti target, the substrate bias voltage was 100V, the Ar flow rate was 400sccm, the vacuum degree was 2.3Pa, the Ti multi-arc target current was 10A, and the deposition time was 7min.

[0044] S5. Functional layer deposition: The Ti magnetron target is turned off, the CrTiAlSiY multi-arc target is turned on, and N2 gas is introduced. The substrate after the Ti nanolayer deposition obtained in S4 is rotated in the furnace to obtain the CrTiAlSiYN nanolayer. The thickness ratio of the CrTiAlSiYN nanolayer to the Ti nanolayer is 1:1.

[0045] The multi-arc target used for functional layer deposition was a CrTiAlSiY target, with a substrate bias voltage of 100V, an N2 flow rate of 1300sccm, a vacuum degree of 4.1Pa, a target current of 100A for the CrTiAlSiY multi-arc target, and a deposition time of 5min.

[0046] S6. Determine the modulation period based on the theoretical thickness of the film, i.e., the number of times S4 and S5 are repeated. Perform a total of 15 cycles to obtain Example 1.

[0047] Example 2 A method for preparing a metal / toughened high-entropy nitride ceramic coating includes the following steps: S1. Pretreatment: Grinding, polishing, and cleaning the substrate; The substrate was a Co3W3 alloy. The wet sandpaper used for grinding the substrate had grits of 400#, 800#, 1200#, 1500#, and 2000#. The corundum powder used for polishing had a particle size of 1μm. The sample surface was bombarded with a pressure of 0.2 MPa. The solvents used for ultrasonic cleaning of the substrate were ethanol and acetone, and the cleaning time was 10 min for each.

[0048] S2. Ion source etching: Ar gas is introduced into a high vacuum environment, and the sample surface under high bias voltage is bombarded by an ion source to remove surface impurities and adsorption. The ion source etching process involves introducing Ar gas into a high vacuum environment with a vacuum level of 0.7 Pa, a temperature of 400 °C, an ion source voltage of 500 V, a substrate bias voltage of 600 V, and an etching time of 20 min, in order to clean and activate the substrate surface.

[0049] S3. Deposit the Ti layer. Turn on the Ti target and deposit Ti layers on the sample surface sequentially using substrate bias values ​​from high to low to obtain the Ti underlayer. The thickness of the Ti underlayer is 200 nm.

[0050] The multi-arc target used for the underlayer deposition was a pure Ti target, with a Ti multi-arc target current of 100A. The substrate bias voltage was set from high to low as 500V / 300V / 200V, and the deposition time was 10min for each. Ar ion etching and underlayer deposition were performed on the substrate surface. The Ar gas flow rate was 180sccm, the vacuum degree was 0.7 Pa, the operating temperature was 400℃, and the rotary table speed was 10r / min.

[0051] S4, Functional layer deposition: Open the Ti magnetron target, introduce Ar gas, and rotate the substrate obtained in S3 after the bottom layer deposition in the furnace to obtain the Ti nanolayer. The magnetron target used for functional layer deposition was a pure Ti target, the substrate bias voltage was 120V, the Ar flow rate was 400sccm, the vacuum degree was 2.3Pa, the Ti magnetron target current was 12A, and the deposition time was 10min.

[0052] S5. Functional layer deposition: The Ti target is turned off, the CrTiAlSiY multi-arc target is turned on, and N2 gas is introduced. The substrate after the Ti functional layer deposition obtained in S4 is rotated in the furnace to obtain the CrTiAlSiYN nanolayer. The thickness ratio of the CrTiAlSiYN nanolayer to the Ti nanolayer is 4:1.

[0053] The multi-arc target used for functional layer deposition was a CrTiAlSiY target, with a substrate bias voltage of 100V, an N2 flow rate of 1300sccm, a vacuum degree of 4.1Pa, a target current of 100A for the CrTiAlSiY multi-arc target, and a deposition time of 20min.

[0054] S6. Determine the modulation period based on the theoretical thickness of the film, i.e., the number of times S4 and S5 are repeated. Perform a total of 5 cycles to obtain Example 2.

[0055] Example 3 A method for preparing a metal / toughened high-entropy nitride ceramic coating includes the following steps: S1. Pretreatment: Grinding, polishing, and cleaning the substrate; The substrate was a Co3W3 alloy. The wet sandpaper used for grinding the substrate had grits of 400#, 800#, 1200#, 1500#, and 2000#. The corundum powder used for polishing had a particle size of 1μm. The sample surface was bombarded with a pressure of 0.2 MPa. The solvents used for ultrasonic cleaning of the substrate were ethanol and acetone, and the cleaning time was 10 min for each.

[0056] S2. Ion source etching: Ar gas is introduced into a high vacuum environment, and the sample surface under high bias voltage is bombarded by an ion source to remove surface impurities and adsorption. The ion source etching process involves introducing Ar gas into a high vacuum environment with a vacuum level of 0.7 Pa, a temperature of 400 °C, an ion source voltage of 500 V, a substrate bias voltage of 600 V, and an etching time of 20 min, in order to clean and activate the substrate surface.

[0057] S3. Ti underlayer deposition: Turn on the metal Ti target and deposit Ti layers on the sample surface sequentially using substrate bias values ​​from high to low to obtain the Ti underlayer; the thickness of the Ti underlayer is 200nm.

[0058] The multi-arc target used for the underlayer deposition was a pure Ti target, with a Ti multi-arc target current of 100A. The substrate bias voltage was set from high to low as 500V / 300V / 200V, and the deposition time was 10min for each. Ar ion etching and underlayer deposition were performed on the substrate surface. The Ar gas flow rate was 180sccm, the vacuum degree was 0.7 Pa, the operating temperature was 400℃, and the rotary table speed was 10r / min.

[0059] S4. Functional layer deposition: Open the Ti magnetron target and introduce Ar gas. The substrate obtained in S3 after the underlayer deposition is rotated in the furnace to obtain the Ti nanolayer; the thickness of the Ti nanolayer is 500 nm.

[0060] The magnetron target used for functional layer deposition was a pure Ti target, the substrate bias voltage was 110V, the Ar flow rate was 450sccm, the vacuum degree was 2.6Pa, the Ti magnetron target current was 8A, and the deposition time was 7min.

[0061] S5. Functional layer deposition: The Ti target is turned off, the CrTiAlSiY multi-arc target is turned on, and N2 gas is introduced. The substrate after the Ti nanolayer deposition obtained in S4 is rotated in the furnace to obtain the CrTiAlSiYN nanolayer. The thickness ratio of the CrTiAlSiYN nanolayer to the Ti nanolayer is 4:1.

[0062] The multi-arc target material used for functional layer deposition was a CrTiAlSiY multi-arc target. The substrate bias voltage was 100V, the N2 flow rate was 1200sccm, the vacuum degree was 4.2Pa, the target current of the CrTiAlSiY multi-arc target was 100A, and the deposition time was 20min.

[0063] S6. Determine the modulation period based on the theoretical thickness of the film, i.e., the number of times S4 and S5 are repeated. Perform a total of 6 cycles to obtain Example 3.

[0064] Example 4 A method for preparing a metal / toughened high-entropy nitride ceramic coating includes the following steps: S1. Pretreatment: Grinding, polishing, and cleaning the substrate; The substrate was selected from nickel-based high-temperature alloy N80A. The wet sandpaper used for substrate grinding had grits of 400#, 800#, 1200#, 1500#, and 2000#. The corundum powder used for polishing had a particle size of 1μm. The sample surface was bombarded with a pressure of 0.2 MPa. The solvents used for ultrasonic cleaning of the substrate were ethanol and acetone, and the cleaning time was 10 min for each.

[0065] S2. Ion source etching: Ar gas is introduced into a high vacuum environment, and the sample surface under high bias voltage is bombarded by an ion source to remove surface impurities and adsorption. The ion source etching process involves introducing Ar gas into a high vacuum environment with a vacuum level of 0.7 Pa, a temperature of 400 °C, an ion source voltage of 500 V, a substrate bias voltage of 600 V, and an etching time of 20 min, in order to clean and activate the substrate surface.

[0066] S3. Bottom layer deposition: Turn on the metal Ti target and sequentially deposit Ti layers on the sample surface using substrate bias values ​​from high to low to obtain the Ti bottom layer; the thickness of the Ti bottom layer is 200nm.

[0067] The multi-arc target used for the bottom layer deposition was a pure Ti target, with a Ti multi-arc target current of 100A. The substrate bias voltage was set from high to low as 500V / 300V / 200V, and the deposition time was 10min for each. Ar ion etching and bottom layer deposition were performed on the substrate surface. The Ar gas flow rate was 180sccm, the vacuum degree was 0.7 Pa, the operating temperature was 400℃, and the rotary table speed was 10r / min.

[0068] S4. Functional layer deposition: Open the Ti magnetron target and introduce Ar gas. The substrate obtained in S3 after the underlayer deposition is rotated in the furnace to obtain the Ti nanolayer; the thickness of the Ti nanolayer is 500 nm.

[0069] The magnetron target used for functional layer deposition was a pure Ti target, the substrate bias voltage was 90V, the Ar flow rate was 450sccm, the vacuum degree was 2.6Pa, the Ti magnetron target current was 15A, and the deposition time was 7min.

[0070] S5. Functional layer deposition: The Ti target is turned off, the CrTiAlSiY multi-arc target is turned on, and N2 gas is introduced. The substrate after the Ti functional layer deposition obtained in S4 is rotated in the furnace to obtain the CrTiAlSiYN nanolayer. The thickness ratio of the CrTiAlSiYN nanolayer to the Ti nanolayer is 4:1.

[0071] The multi-arc target used for functional layer deposition was a CrTiAlSiY target, with a substrate bias voltage of 100V, an N2 flow rate of 1200sccm, a vacuum degree of 4.2Pa, a CrTiAlSiY multi-arc target current of 100A, and a deposition time of 20min.

[0072] S6. Determine the modulation period based on the theoretical thickness of the film, i.e., the number of times S4 and S5 are repeated. Perform a total of 6 cycles to obtain Example 4.

[0073] Comparative Example 1 Compared with Example 1, the coating includes a Ti underlayer and a CrTiAlSiYN nanolayer. The preparation of the Ti underlayer is the same as in Example 1, and the preparation of the CrTiAlSiYN nanolayer is the same as the preparation process of the CrTiAlSiYN nanolayer in Example 1. The thickness is the same as the total thickness of the Ti nanolayer and CrTiAlSiYN nanolayer in Example 1.

[0074] Figure 2These are actual photographs of the Ti / CrTiAlSiYN composite coating prepared according to the method in Example 1. It should be noted that both samples in the image are N80A alloys, and both were prepared using the process described in Example 1. The only difference between them is the size of the substrate sample.

[0075] Figure 4 The figures show the test results of the coating's crack resistance. (a) shows the coating prepared in Comparative Example 1, and (b) shows the Ti / CrTiAlSiYN composite coating prepared in Example 1. Both coatings were tested using a micro Vickers hardness tester. The core principle is to apply a specific test force, press a standard diamond indenter into the surface of the material being tested, measure the diagonal length of the indentation, and calculate the hardness value, referring to the Vickers hardness measurement of metallic materials in GB / T 4340.1-2024. A diamond-shaped indentation was formed on the surface of the diamond indenter sample. The indentation size increased with increasing load, which was 0.025 kg (0.245 N) and 0.05 kg (0.49 N), respectively. Compared with the CrTiAlSiYN single-layer coating in Comparative Example 1 under a 150 kgf indentation load, the composite coating of this invention exhibits superior mechanical properties.

[0076] Similarly, the coatings prepared in Examples 2 to 4 all exhibit excellent crack resistance. The Ti / CrTiAlSiYN nanolayered composite film of the present invention improves upon the columnar crystal defects of single-layer coatings. Compared to the single-layer structure coatings of the prior art, the nanolayered structure formed by the stacking of nano-scale Ti and CrTiAlSiYN sublayers of the present invention helps to hinder the propagation of microcracks within the coating, thus improving the coating's wear resistance. Furthermore, the coating of the present invention is more compact and dense, exhibiting better mechanical properties and is more effective in preventing surface damage caused by high-speed solid particle impacts. Therefore, the present invention has broad application prospects.

[0077] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, it is intended to include any modifications and variations that fall within the scope of the claims and their equivalents.

Claims

1. A metal / toughened high-entropy nitride ceramic coating, characterized in that, The coating consists of a Ti underlayer and a Ti / CrTiAlSiYN functional layer from the inside to the outside of the substrate surface; The Ti / CrTiAlSiYN functional layer is a multilayer structure composed of Ti nanolayers and CrTiAlSiYN nanolayers stacked alternately. The outermost layer of the multilayer structure is the CrTiAlSiYN nanolayer, which is prepared by multi-arc ion plating and has an amorphous nanocrystalline structure. The Ti nanolayer is prepared by magnetron sputtering and has a columnar crystal structure.

2. The metal / toughened high-entropy nitride ceramic coating of claim 1, wherein, In the Ti / CrTiAlSiYN functional layer, a Ti nanolayer or a CrTiAlSiYN nanolayer is first deposited on a Ti substrate.

3. The metal / toughened high-entropy nitride ceramic coating of claim 1, wherein, The thickness of the Ti substrate is 100nm~300nm; The thickness of the Ti nanolayer is 500 nm; the ratio of the thickness of the CrTiAlSiYN nanolayer to the thickness of the Ti nanolayer is 4:1~4; The total thickness of the coating is not less than 15 μm.

4. A method for preparing a metal / toughened high-entropy nitride ceramic coating, characterized in that, The method for preparing the metal / toughened high-entropy nitride ceramic coating of claim 1 includes the following steps: The substrate is ground, polished, and cleaned to obtain the pretreated sample; The surface of the pretreated sample is etched using an ion source to obtain the etched sample. Multi-arc ion plating was used to deposit Ti on the etched sample surface to obtain a Ti underlayer; during the deposition of the Ti underlayer, the substrate bias value was set sequentially from high to low. Depositing a Ti / CrTiAlSiYN functional layer on a Ti substrate: When depositing Ti nanolayers, magnetron sputtering is used to deposit Ti magnetron targets under an inert atmosphere to obtain Ti nanolayers; When depositing CrTiAlSiYN nanolayers, multi-arc ion plating is used to deposit CrTiAlSiY multi-arc targets under a nitrogen atmosphere to obtain CrTiAlSiYN nanolayers. Ti nanolayers and CrTiAlSiYN nanolayers were deposited alternately in cycles to the desired thickness to obtain a metal / toughened high-entropy nitride ceramic coating.

5. The preparation method according to claim 4, characterized in that, First, a Ti nanolayer is deposited on the Ti substrate surface, and then a CrTiAlSiYN nanolayer is deposited on the Ti nanolayer.

6. The preparation method according to claim 4, characterized in that, When depositing Ti nanolayers and CrTiAlSiYN nanolayers, the CrTiAlSiY multi-arc target and the Ti magnetron target are arranged opposite each other. While opening the Ti magnetron target or the CrTiAlSiY multi-arc target, the sample rack is rotated at a constant speed in the furnace.

7. The preparation method according to claim 4, characterized in that, When preparing the Ti substrate, the target material used is a pure Ti multi-arc target, the working gas flow rate is 170 sccm to 190 sccm, the vacuum degree is 0.6 Pa to 0.8 Pa, the substrate bias voltage is 100 V to 600 V, the Ti multi-arc target current is 90 A to 110 A, the deposition temperature is 380 ℃ to 420 ℃, and the deposition time is 5 min to 15 min.

8. The preparation method according to claim 4, characterized in that, When preparing Ti nanolayers and CrTiAlSiYN nanolayers, the target materials used were a pure Ti magnetron target and a CrTiAlSiY multi-arc target, respectively. The working gas flow rate was 400 sccm to 1500 sccm, the vacuum degree was 1.5 Pa to 5 Pa, the substrate bias voltage was 90 V to 120 V, the Ti magnetron target current was 8 A to 15 A, the CrTiAlSiY multi-arc target current was 100 A to 120 A, the total deposition time was 150 min to 200 min, the deposition temperature was 380 ℃ to 420 ℃, and the turntable speed was 8 r / min to 12 r / min.

9. The preparation method according to claim 4, characterized in that, During ion source etching, Ar gas is introduced under vacuum conditions, with a vacuum degree of 0.6 Pa to 0.8 Pa, a temperature of 400 °C, a substrate bias voltage of 550 V to 650 V, and an etching time of 15 min to 25 min.

10. The preparation method according to claim 4, characterized in that, The matrix is ​​made of iron-based heat-resistant steel and nickel-based high-temperature alloy; The wet sandpaper used for sanding has grits of 400#, 800#, 1200#, 1500# and 2000# respectively; The corundum powder used for polishing has a particle size of 0.8μm to 1.2μm, and the sample surface is bombarded with a pressure of 0.3 MPa to 0.6 MPa. The solvents used for cleaning the substrate were ethanol and acetone, and ultrasonic cleaning was performed for 5 to 15 minutes.

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