A nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness and a preparation method thereof

Abstract

The application discloses a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness and a preparation method thereof, and aims at solving the problems of low hardness and poor wear resistance of traditional coatings. The AlNbTiZrN wear-resistant coating is deposited by magnetron sputtering of a high-entropy alloy target, and the atomic percentage content of each element in the wear-resistant coating is as follows: Al is 18.00at%-34.00at%, Nb is 12.00at%-27.00at%, Ti is 10.90at%-13.48at%, Zr is 10.94at%-25.52at%, and N is 32.16at%-48.16at%. The high-entropy alloy coating has high nitrogen content and is composed of an FCC face-centered cubic solid solution phase, and the high-entropy alloy coating has reasonable components, high alloying degree, and good mechanical properties and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high-entropy alloy coating and its preparation, and particularly relates to a nitrogen-saturated AlNbTiZrN high-entropy alloy coating with good mechanical properties and wear resistance and a preparation method thereof. BACKGROUND

[0002] With the extensive application of mechanical devices in traditional handicraft industry and new technology field, the service conditions of key components such as rolling bearings become more and more complex. When facing harsh working conditions such as high speed and heavy load, the surface failure of key components such as rolling bearings becomes a key factor restricting the development of mechanical devices. Without the protection of surface coating, the service life of key components is greatly shortened, so the mechanical and tribological properties of the surface protective coating of key components have important influence on the working performance and service life of key components.

[0003] With the further development of automation in various industries, various surface strengthening technologies have developed rapidly. Traditional coating technologies such as electroplating, which are harmful to the environment, have been gradually eliminated by the times as people's requirements for coating performance and environmental protection continue to improve. However, magnetron sputtering coating has been widely used in recent years due to its high controllability, low deposition temperature, wide range of platable base materials, and good mechanical properties and excellent tribological properties.

[0004] Traditional single metal or alloy coatings are difficult to meet the increasingly stringent requirements in many cases. For example, in the industries of mechanical processing, aerospace, petroleum and chemical engineering, the surfaces of parts are often subjected to high temperature, high pressure, friction, corrosion and other factors. The traditional coating may have problems such as insufficient hardness, poor wear resistance, insufficient corrosion resistance, etc., which leads to the shortening of the service life of the parts, increases the maintenance cost and production risk.

[0005] With the in-depth study of the performance of coating materials, it is found that high-entropy alloy coating has unique structure and excellent performance, and has great application potential in the field of coating. SUMMARY

[0006] The present application is to solve the problems of insufficient hardness, poor wear resistance and insufficient corrosion resistance of traditional coatings, and to provide a high-entropy alloy coating with good mechanical and tribological properties and a preparation method thereof.

[0007] The nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited by magnetron sputtering of an AlNbTiZr target, and is composed of Al, Nb, Ti, Zr and N, with the atomic percentage of each element being: Al: 18.00at% to 34.00at%, Nb: 12.00at% to 27.00at%, Ti: 10.90at% to 13.48at%, Zr: 10.94at% to 25.52at%, and N: 32.16at% to 48.16at%.

[0008] The content of N in the nitrogen-saturated AlNbTiZrN wear-resistant coating is optimized to be 44.33at% to 48.16at%, and the sum of the atomic percentages of Al, Nb, Ti, Zr and N is 100%.

[0009] The preparation method of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is implemented according to the following steps:

[0010] S1, substrate treatment:

[0011] The substrate is cleaned by ultrasonic cleaning with ethanol or acetone, and the cleaned substrate is obtained after drying;

[0012] S2, substrate loading:

[0013] The cleaned substrate is loaded on a rotating tool and sent into a vacuum chamber of a magnetron sputtering device for vacuum pumping;

[0014] S3, heating:

[0015] The vacuum chamber is heated to 200-205℃, and vacuum pumping is performed again;

[0016] S4, substrate cleaning:

[0017] Argon is introduced into the vacuum chamber to perform plasma cleaning of the substrate;

[0018] S5, coating pre-deposition:

[0019] An AlNbTiZr alloy is used as the target material, the argon flow is increased to 100-140sccm, the deposition pressure is controlled to be 0.8-1.5Pa, the voltage of the bias power supply is set to be 100-200V, the bias power supply is turned on, then the direct current pulse power supply is turned on, and pre-deposition is performed for 2-5min;

[0020] S6, coating deposition:

[0021] After the pre-deposition is finished, the direct current pulse power source is kept on, the argon flow rate is gradually reduced, the nitrogen flow rate is gradually increased, the argon flow rate is controlled to be 110-120sccm, the nitrogen flow rate is controlled to be 3-6sccm, the deposition gas pressure is kept to be 0.8-1.5Pa, and the gas phase deposition is carried out;

[0022] S7, cooling: after the temperature of the vacuum chamber is gradually cooled to room temperature, the atmosphere is introduced, the substrate is taken out, and the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0023] In the preparation method of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness, the flow rate of nitrogen needs to be controlled in the process of coating deposition, so that the AlNbTiZr coating reaches a nitrogen (over) saturated state. The Al, Nb, Ti and Zr elements in the AlNbTiZrN wear-resistant coating have high affinity with nitrogen elements, and high content of nitrogen content in the coating is realized under a low nitrogen atmosphere. High nitrogen content makes the lattice atoms inside the coating deviate from the equilibrium position, that is, lattice distortion occurs, thereby increasing the local internal stress, inhibiting the motion of dislocations inside the coating, and the decrease of the average grain size leads to a more dense internal organization of the film, thereby increasing the hardness. The wear resistance of the coating is affected by the hardness, elastic deformation and plastic deformation resistance of the coating, and high nitrogen content makes the coating have higher hardness and fracture toughness, thereby making the coating have better wear resistance. In addition, the oxides and oxide films generated during friction can play a certain lubricating effect, thereby reducing friction and wear, and improving the mechanical properties and wear resistance of the high-entropy alloy coating.

[0024] The nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness and the preparation method thereof have the following beneficial effects:

[0025] 1. The AlNbTiZrN high-entropy alloy coating provided by the application has good mechanical properties and wear resistance, is mainly composed of an FCC solid solution phase, has uniform alloy organization, and has wide application prospects in the field of high-temperature alloy coatings.

[0026] 2. The addition of nitrogen (N) elements in the alloy coating forms a nitride solid solution with an FCC structure, which is beneficial to improving the hardness of the coating.

[0027] 3. The four metal elements of the alloy coating, aluminum (Al), niobium (Nb), titanium (Ti) and zirconium (Zr), can generate TiO2, Nb2O5, Al2O3 and ZrO2 oxides in the friction process, which is beneficial to reducing friction.

[0028] 4、The alloy coating is characterized in that it has a high nitrogen content, the nitrogen content reaches saturation when the nitrogen flow is 12sccm, and with the further increase of the nitrogen content, the nitrogen content tends to be stable, reaching the nitrogen saturation state. This is conducive to improving the hardness and modulus of the AlNbTiZrN coating. The hardness of the AlNbTiZrN high-entropy alloy coating prepared by the application is 9-33GPa, and the elastic modulus is 145-469GPa.

[0029] 5、The AlNbTiZrN high-entropy alloy coating prepared by the application can improve the bonding strength and overall strength of the coating and the substrate, so that the PVD coating exhibits superior mechanical properties and good wear resistance. The friction coefficient of the AlNbTiZrN high-entropy alloy coating prepared by the application is 0.55-0.72, and the wear rate is 8.95x10 -8 ~7.78x10 -7 mm 3 ·N -1 ·mm -1 . BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 X-ray diffraction (XRD) spectrum of the high-entropy alloy coating prepared in Example 1-3;

[0031] Figure 2 Hardness and modulus column chart of the high-entropy alloy coating prepared in Example 1-4;

[0032] Figure 3 Surface scanning electron microscope image of the high-entropy alloy coating prepared in Example 1-4;

[0033] Figure 4 Surface roughness of the high-entropy alloy coating prepared in Example 1-4, wherein (a) represents Example 1, (b) represents Example 2, (c) represents Example 3, and (d) represents Example 4;

[0034] Figure 5 Friction coefficient and wear rate chart of the high-entropy alloy coating prepared in Example 1-3;

[0035] Figure 6 Element content chart of the high-entropy alloy coating prepared in Example 1-4;

[0036] Figure 7 Electron microscope image of the high-entropy alloy coating prepared in Example 1. DETAILED DESCRIPTION

[0037] Specific embodiment one: the preparation method of the high-hardness nitrogen-saturated AlNbTiZrN wear-resistant coating in this embodiment is implemented according to the following steps:

[0038] S1, substrate processing:

[0039] The substrate is ultrasonically cleaned with ethanol or acetone, and after drying, a cleaned substrate is obtained;

[0040] S2, loading the substrate:

[0041] The cleaned substrate is loaded on a rotating tool and sent into the vacuum chamber of the magnetron sputtering device for vacuum pumping;

[0042] S3, heating:

[0043] The vacuum chamber is heated to 200-205°C, and vacuum pumping is performed again;

[0044] S4, substrate cleaning:

[0045] Argon gas is introduced into the vacuum chamber to clean the substrate by plasma;

[0046] S5, coating pre-deposition:

[0047] AlNbTiZr alloy is used as the target material, the argon gas flow is increased to 100-140 sccm, the deposition pressure is controlled at 0.8-1.5 Pa, the voltage of the bias power supply is set to 100-200 V, the bias power supply is turned on, and then the direct current pulse power supply is turned on for pre-deposition for 2-5 min;

[0048] S6, coating deposition:

[0049] After the pre-deposition is completed, the direct current pulse power supply is kept on, the argon gas flow is gradually reduced, the nitrogen gas flow is increased, the argon gas flow is controlled at 110-120 sccm, the nitrogen gas flow is controlled at 3-6 sccm, and the deposition pressure is maintained at 0.8-1.5 Pa for gas phase deposition;

[0050] S7, cooling: When the temperature of the vacuum chamber gradually cools to room temperature, the atmosphere is introduced, the substrate is taken out, and a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0051] The surface roughness of the AlNbTiZrN high-entropy alloy coating prepared in this embodiment is 0.96-7.91 nm.

[0052] The AlNbTiZrN high-entropy alloy coating prepared in this embodiment has an FCC face-centered cubic phase structure, good hardness and wear resistance, and has considerable research value and application potential in the field of high-entropy alloy coatings.

[0053] The AlNbTiZrN high-entropy alloy coating prepared in this embodiment has reasonable composition, high alloying degree, and good mechanical properties and wear resistance, meeting the requirements for surface protection of extreme environment components such as cutters, bearings, gears, and drill bits.

[0054] Specific embodiment two: the difference between this embodiment and the specific embodiment one is that the material of the substrate in step S1 is single metal, ceramic or alloy material.

[0055] Specific embodiment three: the difference between this embodiment and the specific embodiment one or two is that the time of ultrasonic cleaning in step S1 is 20-30 min.

[0056] Specific embodiment four: the difference between this embodiment and one of the specific embodiments one to three is that the vacuum is extracted again to 3x10 -3 Pa in step S3.

[0057] Specific embodiment five: the difference between this embodiment and one of the specific embodiments one to four is that the plasma cleaning process in step S4 is as follows:

[0058] argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is controlled to be 17 sccm, the ion source power is first turned on, the surface of the substrate is cleaned using the ion source for 10-20 min, then the ion source power is turned off, the bias power is turned on, and the bias cleaning is performed for 10-20 min.

[0059] Specific embodiment six: the difference between this embodiment and the specific embodiment five is that the ion source power parameters are set as follows: the current is 0.3 A, and the duty cycle is 70%.

[0060] Specific embodiment seven: the difference between this embodiment and the specific embodiment five is that the bias power parameters are set as follows: the voltage is 800 V, and the duty cycle is 50%.

[0061] Specific embodiment eight: the difference between this embodiment and one of the specific embodiments one to seven is that the direct current pulse power parameters are controlled as follows: the power is 800-1200 W, and the duty cycle is 70% in step S5.

[0062] Specific embodiment nine: the difference between this embodiment and one of the specific embodiments one to eight is that the flow rate of the argon gas is controlled to be 100-105 sccm, the flow rate of the nitrogen gas is controlled to be 15-20 sccm, the deposition gas pressure is maintained to be 1.0 Pa, and the gas phase deposition is performed in step S6.

[0063] The content of the argon gas and the nitrogen gas in the gas phase deposition process is optimized in this embodiment, so that the wear resistance of the nitrogen-saturated AlNbTiZrN wear-resistant coating reaches the best.

[0064] Specific embodiment ten: the difference between this embodiment and one of the specific embodiments one to nine is that the thickness of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is 2.5-6.0 μm in step S7.

[0065] Embodiment one: the preparation method of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness in the embodiment is implemented according to the following steps:

[0066] S1, substrate treatment:

[0067] The substrate is cleaned with ethanol for 20 min, and the cleaned substrate is obtained after drying. The substrate is made of 316 stainless steel and has a size of 30 mm x 20 mm x 2 mm.

[0068] S2, substrate loading:

[0069] The cleaned substrate is loaded on a rotating tool and sent into a vacuum chamber of a magnetron sputtering device. The vacuum chamber is vacuumized to 5 x 10 -3 Pa;

[0070] S3, heating:

[0071] The vacuum chamber is heated to 200℃, and vacuumized to 3 x 10 -3 Pa again;

[0072] S4, substrate cleaning:

[0073] Argon gas is introduced into the vacuum chamber at a flow rate of 17 sccm. The ion source power is turned on to clean the surface of the substrate for 15 min. Then, the ion source power is turned off, the bias power is turned on, and the substrate is cleaned for 15 min. The bias power is turned off, and the substrate is plasma cleaned.

[0074] S5, coating pre-deposition:

[0075] The AlNbTiZr alloy is used as the target material. The argon gas flow rate is increased to 120 sccm, the deposition gas pressure is controlled to be 1.0 Pa, the voltage of the bias power is set to be 100 V, the bias power is turned on, and then the direct current pulse power is turned on for pre-deposition for 3 min.

[0076] S6, coating deposition:

[0077] After the pre-deposition is completed, the direct current pulse power and the bias power are kept on. The argon gas flow rate is gradually reduced, the nitrogen gas flow rate is gradually increased, the argon gas flow rate is controlled to be 116 sccm, the nitrogen gas flow rate is controlled to be 4 sccm, the deposition gas pressure is kept to be 1.0 Pa, and the gas phase deposition is performed for 90 min.

[0078] S7, cooling: After the temperature of the vacuum chamber is gradually cooled to room temperature, the substrate is taken out after the atmosphere is introduced, and the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0079] In step S4 of the embodiment, the ion source power supply parameters are set as follows: current is 0.3 A, and duty cycle is 70%; the bias power supply parameters are set as follows: voltage is 800 V, and duty cycle is 50%. In step S5, the direct current pulse power supply parameters are set as follows: power is 1000 W, and duty cycle is 70%.

[0080] The purity of argon used in the embodiment is 99.99%, and the purity of nitrogen is 99.99%.

[0081] The XRD pattern of the AlNbTiZrN high-entropy alloy coating prepared in the embodiment is shown in Figure 1 It can be seen from the figure that the high-entropy alloy composition has an FCC phase structure.

[0082] The hardness curve of the AlNbTiZrN high-entropy alloy coating is shown in Figure 2 It can be seen from the figure that the hardness of the AlNbTiZrN high-entropy alloy coating reaches 32.95 GPa, and the modulus reaches 468.67 GPa.

[0083] The surface scanning electron microscope image of the AlNbTiZrN high-entropy alloy coating is shown in Figure 3 The surface quality is good, and there is no cracking and peeling.

[0084] The surface roughness of the AlNbTiZrN high-entropy alloy coating is shown in Figure 4 The surface roughness is only 4.35 nm.

[0085] The friction coefficient and wear rate of the AlNbTiZrN high-entropy alloy coating are shown in Figure 5 The friction coefficient is 0.6, and the wear rate is only 9.27 x 10 -8 mm 3 ·N -1 ·mm -1 .

[0086] The content of each element of the AlNbTiZrN high-entropy alloy coating is shown in Figure 6 The nitrogen content is 44.33 at.%.

[0087] Embodiment two: the preparation method of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness in the embodiment is implemented according to the following steps:

[0088] S1, substrate treatment:

[0089] The substrate is cleaned with ethanol for 20 min, and the cleaned substrate is obtained after drying. The substrate is made of 316 stainless steel, and the size is 30 mm x 20 mm x 2 mm.

[0090] S2, loading:

[0091] The cleaned substrate is mounted on a rotating tool and sent into a vacuum chamber of a magnetron sputtering device, vacuumized to 5x10 -3 Pa;

[0092] S3, heating:

[0093] The vacuum chamber is heated to 200℃, and vacuumized again to 3x10 -3 Pa;

[0094] S4, substrate cleaning:

[0095] The vacuum chamber is filled with argon gas, and the argon gas flow is controlled to be 17sccm. The ion source power is turned on first, and the substrate surface is cleaned for 15min using the ion source. Then the ion source power is turned off, the bias power is turned on, and the substrate is cleaned for 15min using the bias. The plasma cleaning is completed.

[0096] S5, coating pre-deposition:

[0097] The AlNbTiZr alloy is used as the target material, the argon gas flow is increased to 120sccm, the deposition pressure is controlled to be 1.0Pa, the voltage of the bias power is set to be 100V, the bias power is turned on, and then the direct current pulse power is turned on for pre-deposition for 3min.

[0098] S6, coating deposition:

[0099] After the pre-deposition is completed, the direct current pulse power and the bias power are kept on, the argon gas flow is gradually reduced, the nitrogen gas flow is gradually increased, the argon gas flow is controlled to be 100sccm, the nitrogen gas flow is controlled to be 20sccm, the deposition pressure is kept at 1.0Pa, and the vapor deposition is performed for 90min.

[0100] S7, cooling: After the temperature of the vacuum chamber is gradually cooled to room temperature, the atmosphere is introduced, the substrate is taken out, and the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0101] In step S4 of this embodiment, the ion source power parameters are set as follows: the current is 0.3A, and the duty cycle is 70%; the bias power parameters are set as follows: the voltage is 800V, and the duty cycle is 50%. In step S5, the direct current pulse power parameters are set as follows: the power is 1000W, and the duty cycle is 70%.

[0102] The XRD pattern of the AlNbTiZrN high-entropy alloy coating prepared in this embodiment is shown in Figure 1 It can be seen that the high-entropy alloy composition has an FCC phase structure.

[0103] The hardness curve of the AlNbTiZrN high-entropy alloy coating is shown in Figure 2As shown, the hardness of the AlNbTiZrN high-entropy alloy coating reaches 28.92 GPa, and the modulus reaches 359.14 GPa.

[0104] The surface scanning electron microscope image of the AlNbTiZrN high-entropy alloy coating is as shown in the figure. Figure 3 As shown, the surface quality is good, and there is no cracking and peeling.

[0105] The surface roughness of the AlNbTiZrN high-entropy alloy coating is as shown in the figure. Figure 4 As shown, the surface roughness is only 3.26 nm.

[0106] The friction coefficient and wear rate of the AlNbTiZrN high-entropy alloy coating are as shown in the figure. Figure 5 As shown, the friction coefficient is 0.5, and the wear rate is only 8.95x10 -8 mm 3 ·N -1 ·mm -1 The mechanical properties and wear resistance of the AlNbTiZrN high-entropy alloy coating obtained in this embodiment are the best.

[0107] The content of each element of the AlNbTiZrN high-entropy alloy coating is as shown in the figure. Figure 6 As shown, the nitrogen content is 46.47 at. %.

[0108] Embodiment three: the preparation method of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness in this embodiment is implemented according to the following steps:

[0109] S1, substrate treatment:

[0110] Ethanol is used to ultrasonically clean the substrate for 20 min, and the cleaned substrate is obtained after drying. The substrate is made of 316 stainless steel and has a size of 30 mm x 20 mm x 2 mm.

[0111] S2, loading:

[0112] The cleaned substrate is loaded on a rotating tool and sent into the vacuum chamber of a magnetron sputtering device. The vacuum chamber is evacuated to 5x10 -3 Pa.

[0113] S3, heating:

[0114] The vacuum chamber is heated to 200℃, and then evacuated to 3x10 -3 Pa.

[0115] S4, substrate cleaning:

[0116] The argon gas is introduced into the vacuum chamber, the argon gas flow is controlled to be 17 sccm, the ion source power is turned on first, the surface of the substrate is cleaned by the ion source for 15 min, then the ion source power is turned off, the bias power is turned on, the substrate is cleaned by the bias for 15 min, and the bias power is turned off, and the substrate is cleaned by the plasma;

[0117] S5, coating pre-deposition:

[0118] The argon gas flow is increased to 120 sccm, the deposition pressure is controlled to be 1.0 Pa, the voltage of the bias power is set to be 100 V, the bias power is turned on, then the direct current pulse power is turned on, and pre-deposition is performed for 3 min.

[0119] S6, coating deposition:

[0120] After the pre-deposition is completed, the direct current pulse power and the bias power are kept on, the argon gas flow is gradually reduced, the nitrogen gas flow is increased, the argon gas flow is controlled to be 108 sccm, the nitrogen gas flow is controlled to be 12 sccm, the deposition pressure is kept to be 1.0 Pa, and vapor deposition is performed for 90 min.

[0121] S7, cooling: after the temperature of the vacuum chamber is gradually cooled to room temperature, the atmosphere is introduced, the substrate is taken out, and the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0122] In step S4 of this embodiment, the ion source power parameters are set as follows: current: 0.3 A, duty cycle: 70%; the bias power parameters are set as follows: voltage: 800 V, duty cycle: 50%. In step S5, the direct current pulse power parameters are set as follows: power: 1000 W, duty cycle: 70%.

[0123] The XRD pattern of the AlNbTiZrN high-entropy alloy coating prepared in this embodiment is shown in Figure 1 It can be seen that the high-entropy alloy composition has an FCC phase structure.

[0124] The hardness curve of the AlNbTiZrN high-entropy alloy coating is shown in Figure 2 It can be seen that the hardness of the AlNbTiZrN high-entropy alloy coating reaches 29.38 GPa, and the modulus reaches 378.89 GPa.

[0125] The surface scanning electron microscope image of the AlNbTiZrN high-entropy alloy coating is shown in Figure 3 The surface quality is good, and there is no cracking and peeling.

[0126] The surface roughness of the AlNbTiZrN high-entropy alloy coating is shown in Figure 4 The surface roughness is only 3.45 nm.

[0127] The AlNbTiZrN high-entropy alloy coating has a friction coefficient and a wear rate as shown in Table 1. Figure 5 The friction coefficient is 0.6 and the wear rate is only 9.75x10 -8 mm 3 ·N -1 ·mm -1 .

[0128] The AlNbTiZrN high-entropy alloy coating has an element content as shown in Table 2. Figure 6 The nitrogen content is 47.44at.%.

[0129] The preparation method of the high-hardness nitrogen-saturated AlNbTiZrN wear-resistant coating of the comparative example is implemented according to the following steps.

[0130] S1, substrate treatment:

[0131] The substrate is ultrasonically cleaned with ethanol for 20 min, and the cleaned substrate is obtained after drying. The substrate is made of 316 stainless steel and has a size of 30 mm x 20 mm x 2 mm.

[0132] S2, substrate loading:

[0133] The cleaned substrate is loaded on a rotating tool and sent into a vacuum chamber of a magnetron sputtering device. The vacuum chamber is vacuumized to 5x10 -3 Pa.

[0134] S3, heating:

[0135] The vacuum chamber is heated to 200℃, and vacuumized again to 3x10 -3 Pa.

[0136] S4, substrate cleaning:

[0137] Argon gas is introduced into the vacuum chamber at a flow rate of 17sccm. The ion source power is turned on to clean the surface of the substrate for 15 min. Then, the bias power is turned on to clean the surface of the substrate for 15 min. The bias power is turned off, and the substrate is plasma cleaned.

[0138] S5, coating pre-deposition:

[0139] The AlNbTiZr alloy is used as the target material. The argon flow rate is increased to 120sccm, the deposition pressure is controlled at 1.0Pa, the voltage of the bias power is set at 100V, the bias power is turned on, and then the direct current pulse power is turned on for pre-deposition for 3 min.

[0140] S6, coating deposition:

[0141] After the pre-deposition is completed, the direct current pulse power supply and the bias power supply are kept on, the argon flow rate is gradually reduced, the nitrogen flow rate is gradually increased, the argon flow rate is controlled to be 120 sccm, the nitrogen flow rate is controlled to be 0 sccm, the deposition pressure is kept to be 1.0 Pa, and the vapor deposition is performed for 90 min;

[0142] S7, cooling: after the temperature of the vacuum chamber is gradually cooled to room temperature, the atmosphere is introduced, the substrate is taken out, and the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

[0143] In step S4 of the embodiment, the ion source power supply parameters are set as follows: current: 0.3 A, and duty cycle: 70%; and the bias power supply parameters are set as follows: voltage: 800 V, and duty cycle: 50%. In step S5, the direct current pulse power supply parameters are set as follows: power: 1000 W, and duty cycle: 70%.

[0144] The hardness curve of the AlNbTiZrN high-entropy alloy coating prepared in the embodiment is shown in Figure 2 It can be seen from the figure that the hardness of the AlNbTiZrN high-entropy alloy coating reaches 9.61 GPa, and the modulus reaches 145.53 GPa.

[0145] The scanning electron microscope image of the surface of the AlNbTiZrN high-entropy alloy coating is shown in Figure 3 It can be seen from the figure that the surface quality of the AlNbTiZrN high-entropy alloy coating is good, and there is no cracking and peeling.

[0146] The surface roughness of the AlNbTiZrN high-entropy alloy coating is shown in Figure 4 It can be seen from the figure that the surface roughness of the AlNbTiZrN high-entropy alloy coating is only 0.96 nm.

[0147] The friction coefficient and the wear rate of the AlNbTiZrN high-entropy alloy coating are shown in Figure 5 It can be seen from the figure that the friction coefficient of the AlNbTiZrN high-entropy alloy coating is 0.7, and the wear rate is only 7.78×10 -7 mm 3 ·N -1 ·mm -1 .

[0148] The content of each element of the AlNbTiZrN high-entropy alloy coating is shown in Figure 6 It can be seen from the figure that the nitrogen content of the AlNbTiZrN high-entropy alloy coating is 0.

[0149] Although the embodiments of the present application have been shown and described, it can be understood by those of ordinary skill in the art that various changes, modifications, replacements and variations can be made to the embodiments without departing from the principles and spirits of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness, characterized in that The nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited by magnetron sputtering of an AlNbTiZr target, and is composed of Al, Nb, Ti, Zr and N, with the atomic percentage of each element being: Al: 18.00 at% to 34.00 at%, Nb: 12.00 at% to 27.00 at%, Ti: 10.90 at% to 13.48 at%, Zr: 10.94 at% to 25.52 at%, and N: 44.33 at% to 48.16 at%.

2. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 1, characterized in that The preparation method is implemented according to the following steps: S1, substrate treatment: The substrate is cleaned by ultrasonic cleaning with ethanol or acetone, and dried to obtain a cleaned substrate; S2, substrate loading: The cleaned substrate is loaded on a rotating tool and sent into a vacuum chamber of a magnetron sputtering device for vacuum pumping; S3, heating: The vacuum chamber is heated to 200-205 DEG C, and vacuum pumping is performed again; S4, substrate cleaning: Argon gas is introduced into the vacuum chamber to perform plasma cleaning of the substrate; S5, coating pre-deposition: An AlNbTiZr alloy is used as the target material, the argon gas flow is increased to 100-140 sccm, the deposition pressure is controlled to be 0.8-1.5 Pa, the voltage of the bias power supply is set to 100-200 V, the bias power supply is turned on, and then the direct current pulse power supply is turned on for pre-deposition for 2-5 min; S6, coating deposition: After the pre-deposition is completed, the direct current pulse power supply is kept on, the argon gas flow is gradually reduced, the nitrogen gas flow is increased, the argon gas flow is controlled to be 100-105 sccm, the nitrogen gas flow is controlled to be 15-20 sccm, the AlNbTiZr coating is brought to a nitrogen-saturated state, the deposition pressure is maintained at 1.0 Pa, and gas phase deposition is performed; S7, cooling:

3. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 2, characterized in that After the temperature of the vacuum chamber gradually cools to room temperature, the atmosphere is introduced, the substrate is taken out, and a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness is deposited on the substrate.

4. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 2, characterized in that In step S3 the vacuum is again reduced to 3 x 10 -3 Pa.

5. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 2, characterized in that The material of the substrate in step S1 is elemental metal, ceramic or alloy material. The plasma cleaning process in step S4 is as follows:

6. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 5, characterized in that Argon gas is introduced into the vacuum chamber, the argon gas flow is controlled to be 17 sccm, the ion source power supply is first turned on, the ion source is used to clean the surface of the substrate for 10-20 min, then the ion source power supply is turned off, the bias power supply is turned on, and the bias cleaning is performed for 10-20 min.

7. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 5, characterized in that The ion source power supply parameters are set as follows: current is 0.3 A, and duty cycle is 70%.

8. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 2, characterized in that The bias power supply parameters are set as follows: voltage is 800 V, and duty cycle is 50%.

9. The method of producing a nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness according to claim 2, characterized in that The direct current pulse power supply parameters in step S5 are set as follows: power is 800-1200 W, and duty cycle is 70%. The thickness of the nitrogen-saturated AlNbTiZrN wear-resistant coating with high hardness in step S7 is 2.5-6.0 μm.

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