Anti-radiation high-entropy alloy nitride hard film and preparation method thereof

Abstract

The invention provides an anti-radiation high-entropy alloy nitride hard film and a preparation method thereof, the molecular formula of high-entropy alloy nitride in the hard film is TiaCrbSicWdTaeGdfNx, a = 8-15, b = 8-15, c = 6-12, d = 6-12, e = 6-8, f = 6-8, x = 30-50, and a + b + c + d + e + f + x = 100. The preparation method comprises the following steps: preparing a pure Ti target material and a TiCrSiWTaGd high-entropy alloy target material; preparing a substrate and pretreating to a to-be-coated state; performing sputter coating on the substrate by using a Ti target material to obtain a TiN transition layer on the surface of the substrate; and a TiCrSiWTaGd high-entropy alloy target material is used for conducting sputtering coating on the TiN transition layer, and the high-entropy alloy nitride hard thin film is obtained. The problem that radiation resistance, high hardness, high wear resistance and high stability of the spacecraft material surface cannot be considered at the same time is solved, and the requirement for radiation protection of the spacecraft surface is met.

Description

Technical Field

[0001] This invention belongs to the field of space protection film technology, and relates to radiation-resistant high-entropy nitride hard films, particularly to a radiation-resistant high-entropy alloy nitride hard film and its preparation method, which can meet the wear-resistant protection requirements under high-energy particle irradiation conditions in space. Background Technology

[0002] In manned spaceflight, deep space exploration and other missions, spacecraft need to be exposed to high-energy particle radiation environments for a long time, including high-energy electrons, protons, neutrons, gamma rays and other cosmic rays from the solar wind and magnetosphere. These particles can cause the accumulation of material defects and a significant reduction in properties such as strength and hardness. Therefore, it is urgent to construct radiation-resistant, high-hardness and high-stability radiation-resistant hard materials on the surface of key parts of spacecraft (such as antennas, shells, optical devices and sensors). Traditional thin film materials such as TiN, CrN and Si3N4 often face a series of shortcomings under high radiation doses, such as lattice structure destruction or amorphization and insufficient wear resistance, which cannot meet the urgent needs of space exploration missions in extreme environments of long-term high-energy particle radiation. Summary of the Invention

[0003] In order to overcome the shortcomings of the existing technology, the inventors have conducted intensive research and provided a radiation-resistant high-entropy alloy nitride hard film and its preparation method, which solves the problem that the radiation resistance, high hardness, high wear resistance and high stability of spacecraft material surfaces cannot be achieved at the same time, and meets the radiation protection requirements of spacecraft surfaces.

[0004] Compared to traditional hard thin film materials, high-entropy alloy thin films, through lattice mismatch and high mixing entropy, delay dislocation movement and vacancy aggregation, maintaining a highly stable structure under high radiation doses, thus preserving extremely high performance stability. Nitrides of Ti, Cr, and Si possess high hardness, significantly improving the material's hardness and wear resistance. W exhibits high resistance to neutron and proton radiation, Ta demonstrates high radiation stability at high temperatures, and Gd exhibits excellent neutron absorption properties. By introducing radiation-resistant elements such as W, Ta, and Gd into Ti, Cr, and Si and forming nitrides, thin films can simultaneously possess a series of advantages including high hardness, high wear resistance, resistance to high-energy particle radiation in space environments, and high stability, making them promising for future applications in space-based radiation-resistant hard thin film materials.

[0005] The technical solution provided by this invention is as follows:

[0006] In a first aspect, a radiation-resistant high-entropy alloy nitride hard film, wherein the high-entropy alloy nitride in the hard film has the molecular formula Ti. a Cr b Si c W d Tae Gd f N x , where a=8~15, b=8~15, c=6~12, d=6~12, e=6~8, f=6~8, x=30~50, a+b+c+d+e+f+x=100.

[0007] Secondly, a method for preparing a radiation-resistant high-entropy alloy nitride hard thin film includes the following steps:

[0008] Prepare pure Ti target materials and TiCrSiWTaGd high-entropy alloy target materials;

[0009] Prepare the substrate and pre-treat it to the state to be coated;

[0010] A TiN transition layer is obtained on the substrate surface by sputtering a Ti target.

[0011] High-entropy alloy nitride hard films were obtained by sputtering coating on TiN transition layers using TiCrSiWTaGd high-entropy alloy targets.

[0012] Thirdly, a radiation-resistant and wear-resistant protective layer includes a base layer and a top layer, wherein the base layer is located between the substrate and the top layer and is made of TiN, and the top layer is made of Ti. a Cr b Si c W d Ta e Gd f N x Layer, where a = 8–15, b = 8–15, c = 6–12, d = 6–12, e = 6–8, f = 6–8, x = 30–50, a+b+c+d+e+f+x = 100.

[0013] The radiation-resistant high-entropy alloy nitride hard thin film and its preparation method provided by the present invention have the following beneficial effects:

[0014] (1) The present invention provides a radiation-resistant high-entropy alloy nitride hard film. Through the cocktail effect of high-entropy alloy, Ti, Cr and Si nitride elements bring the film extremely high hardness, W element has high resistance to neutron and proton irradiation, Ta element has the characteristic of radiation resistance stability at high temperature, and Gd element has excellent shielding and neutron absorption performance. The multi-principal high-entropy alloy nitride film formed has high lattice distortion and local complex structure, which can effectively suppress radiation-induced material defects, maintain high stability, and improve overall radiation resistance.

[0015] (2) The radiation-resistant high-entropy alloy nitride hard film provided by the present invention exhibits a high hardness of 37-63 GPa and can maintain good mechanical integrity under extreme thermal-radiation coupling environment, which helps to resist the erosion of spacecraft surface by micro-meteorites and high-speed space dust; the synergistic strengthening mechanism of multiple elements such as Ti, Cr, Si, W, Ta and Gd improves the material’s structural stability under high temperature conditions, and maintains the phase structure and performance without degradation in the area of ​​strong solar radiation or high-temperature airflow scouring of the thruster.

[0016] (3) The present invention provides a method for preparing a radiation-resistant high-entropy alloy nitride hard film. By designing a TiN transition layer between the substrate and the TiCrSiWTaGd high-entropy alloy nitride film, the lattice parameter mismatch between the substrate and the TiCrSiWTaGd high-entropy alloy nitride film is reduced, and the film-substrate bonding is improved.

[0017] (4) The present invention provides a method for preparing a radiation-resistant high-entropy alloy nitride hard film. The high-entropy alloy nitride film is deposited on a variety of substrates by magnetron sputtering, which will not bring additional significant weight to the spacecraft and is conducive to its widespread application. Attached Figure Description

[0018] Figure 1 The SEM images show the surface and cross-sectional microstructure of the TiCrSiWTaGd high-entropy alloy nitride hard thin film in Example 1.

[0019] Figure 2 The friction coefficient and wear rate of the TiCrSiWTaGd high-entropy alloy nitride hard films before and after irradiation in Examples 1-4 and the TiN film in Comparative Example 1 are shown. Detailed Implementation

[0020] The features and advantages of the present invention will become clearer and more apparent from the following detailed description.

[0021] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments.

[0022] This invention provides a radiation-resistant high-entropy alloy nitride hard film, wherein the high-entropy alloy nitride in the hard film has the molecular formula Ti. a Cr b Si c W d Ta e Gd f N xWhere a = 8–15, b = 8–15, c = 6–12, d = 6–12, e = 6–8, f = 6–8, x = 30–50, a+b+c+d+e+f+x = 100; the high-entropy alloy nitride has an FCC (face-centered cubic) structure.

[0023] The overall thickness of the hard film is 2.5 to 4.5 μm, and the surface nanohardness is not less than 30 GPa, preferably 37 to 63 GPa.

[0024] When the nitrogen content in the high-entropy alloy nitride of the hard film is x = 45 to 50, the bonding between the metal atoms and nitrogen atoms reaches saturation, and the nanohardness of the hard film reaches 50 to 63 GPa.

[0025] TiCrSiWTaGd high-entropy alloy nitride hard films exhibit excellent radiation resistance stability. After irradiation tests conducted using ground-based ionization irradiation simulation equipment, the crystal structure remains unchanged, and the surface nano-hardness and wear resistance do not decrease.

[0026] This invention also provides a method for preparing a radiation-resistant high-entropy alloy nitride hard thin film, comprising the following steps:

[0027] S1. Prepare the target material: There are two types of targets. One is a pure Ti target. The other is a TiCrSiWTaGd high-entropy alloy target containing six elements: Ti, Cr, Si, W, Ta, and Gd. The atomic ratio of each element is Ti:Cr:Si:W:Ta:Gd = a':b':c':d':e':f', where a' = 10~30, b' = 10~30, c' = 5~20, d' = 5~15, e' = 5~10, f' = 5~10, and a'+b'+c'+d'+e'+f' = 100.

[0028] Ti targets were obtained by vacuum melting, while TiCrSiWTaGd high-entropy alloy targets were prepared by powder metallurgy.

[0029] S2, Prepare the base.

[0030] The substrate is one of titanium alloy, aluminum alloy, aluminum-lithium alloy, or magnesium alloy. Before coating, the substrate surface is ground and polished, then wiped with alcohol, and then ultrasonically cleaned.

[0031] S3, sputtered deposition of thin film:

[0032] S31, turn on the magnetron sputtering equipment, load the substrate and target as required, evacuate the sputtering chamber, and introduce pure Ar protective gas.

[0033] S32, open the sample stage valve and maintain the sample stage speed at 10-20 rpm (e.g., 15 rpm), turn on the negative bias voltage of -100-200V (e.g., -150V) to clean the substrate, and pre-sputter the Ti target and TiCrSiWTaGd high-entropy alloy target to remove impurities and contaminants from the surface of the Ti target and TiCrSiWTaGd high-entropy alloy target.

[0034] S33, perform TiN transition layer sputtering, introduce N2, adjust the Ar and N2 gas flow rate ratio in the mixed gas to 1:3 to 1:5, the total gas flow rate to 50 to 80 sccm, the working gas pressure to 0.1 to 1.0 Pa, adjust the DC sputtering power of the Ti target to 150 to 250 W, perform sputtering coating on the substrate, the sputtering time to 20 to 40 min, and a TiN transition layer can be obtained on the substrate surface after sputtering.

[0035] For example, N2 is introduced, the flow ratio of Ar and N2 in the mixed gas is adjusted to 1:4, the total gas flow rate is 60 sccm, the working gas pressure is 0.5 Pa, the DC sputtering power of the Ti target is adjusted to 200 W, the substrate is sputtered and coated, the sputtering time is 30 min, and a TiN transition layer can be obtained on the substrate surface after sputtering.

[0036] After sputtering the TiN transition layer (S34), adjust the flow rate ratio of Ar and N2 in the mixed gas to 3:1 to 1:3, and the total flow rate of the Ar and N2 mixed gas to 60 to 100 sccm (e.g., 80 sccm). Then, adjust the DC sputtering power of the TiCrSiWTaGd high-entropy alloy target to 300 to 600 W to ensure that the target can glow. Sputter the substrate and deposit a film. After sputtering, a TiCrSiWTaGd high-entropy alloy nitride hard film can be obtained on the TiN transition layer of the substrate.

[0037] Example

[0038] Example 1

[0039] A method for preparing a radiation-resistant high-entropy alloy nitride hard thin film, characterized by comprising the following steps:

[0040] (1) Target preparation: Pure Ti target with a purity of 99.99% and a size of 101.6 mm, prepared by vacuum melting, and TiCrSiWTaGd high-entropy alloy target with a purity of 99.99% and a size of 101.6 mm, prepared by powder metallurgy, were selected. Ti:Cr:Si:W:Ta:Gd=a':b':c':d':e':f', where a'=28, b'=26, c'=17, d'=12, e'=9, f'=8, a'+b'+c'+d'+e'+f'=100.

[0041] (2) Substrate Preparation: In this embodiment, a purchased polished single-crystal silicon (100) substrate and TC4 titanium alloy were selected. The single-crystal silicon substrate was used for morphological observation and crystal structure testing of TiCrSiWTaGd high-entropy alloy nitride thin films, while the TC4 titanium alloy substrate was used for testing the nanohardness, friction coefficient, and wear rate of the thin films. For the TC4 titanium alloy, the TC4 titanium alloy rod was first cut into two Φ40×10mm circular substrates using a wire cutting device. Then, the scratches formed by cutting were removed by sequentially polishing with metallographic sandpaper of grades 180#, 400#, 600#, 800#, and 1600#. Then, it was polished to a mirror finish with diamond polishing paste of different grades W5 and W2.5, and then wiped with anhydrous ethanol. Finally, the single-crystal silicon and TC4 titanium alloy substrates were ultrasonically cleaned for 10 minutes and dried.

[0042] (3) Install the substrate and target material into the sample stage and sputtering source position in the vacuum chamber of the magnetron sputtering equipment, respectively.

[0043] (4) Close the vacuum chamber, turn on the chiller and vacuum gauge, and first turn on the mechanical pump to perform a rough vacuum in the vacuum chamber until the pressure reaches 2×10⁻⁶. -3 When the pressure reaches 5 Pa, the molecular pump is turned on to further evacuate the vacuum, until the vacuum reaches 5 × 10⁻⁶ Pa. -4 Pa.

[0044] (5) After vacuuming, open the sample stage valve and maintain the sample stage speed at 15 rpm. Turn on the negative bias voltage -150V to clean the substrate for 15 minutes. Keep the sputtering target baffle closed, introduce pure Ar gas, and adjust the DC power of the Ti target and TiCrSiWTaGd high-entropy alloy target to 200W and 300W respectively for pre-sputtering. The pre-sputtering time is 5 minutes to remove impurities and contaminants from the target surface.

[0045] (6) After pre-sputtering, N2 is introduced, and the flow rate ratio of Ar and N2 in the mixed gas is adjusted to 1:4. The total gas flow rate is 60 sccm, the working pressure is 0.5 Pa, the DC sputtering power of Ti target is adjusted to 200 W, the Ti sputtering target baffle is opened, and the substrate is sputtered and coated. The sputtering time is 30 min. After sputtering, a TiN transition layer can be obtained on the sample surface.

[0046] (7) Adjust the Ar:N2 mixed gas flow ratio to 3:1, the total flow rate of the Ar and N2 mixed gas is 80 sccm, the working gas pressure is 0.5 Pa, the power of the TiCrSiWTaGd high-entropy alloy target is 300 W, the TiCrSiWTaGd high-entropy alloy sputtering target baffle is opened, and the sputtering time is 240 min, depositing a TiCrSiWTaGd high-entropy alloy nitride film on the substrate surface. The molecular formula of the high-entropy alloy nitride in the two TC4 titanium alloy substrate hard films is Ti 13 Cr 12 Si7W8Ta7Gd7N 46 The FCC structure has a film thickness of 3 μm. Figure 1 The SEM images show the surface and cross-sectional microstructure of the TiCrSiWTaGd high-entropy alloy nitride hard film in Example 1.

[0047] Example 2

[0048] A method for preparing a radiation-resistant high-entropy alloy nitride hard thin film, characterized by comprising the following steps:

[0049] (1) Target preparation: Pure Ti target with a purity of 99.99% and a size of 101.6 mm, prepared by vacuum melting, and TiCrSiWTaGd high-entropy alloy target with a purity of 99.99% and a size of 101.6 mm, prepared by powder metallurgy, were selected. Ti:Cr:Si:W:Ta:Gd=a':b':c':d':e':f', where a'=25, b'=23, c'=20, d'=14, e'=9, f'=9, a'+b'+c'+d'+e'+f'=100.

[0050] (2) Substrate Preparation: In this embodiment, a purchased polished single-crystal silicon (100) substrate and TC4 titanium alloy were selected. The single-crystal silicon substrate was used for morphological observation and crystal structure testing of TiCrSiWTaGd high-entropy alloy nitride thin films, while the TC4 titanium alloy substrate was used for testing the nanohardness, friction coefficient, and wear rate of the thin films. For the TC4 titanium alloy, the TC4 titanium alloy rod was first cut into two Φ40×10mm circular substrates using a wire cutting device. Then, the scratches formed by cutting were removed by sequentially polishing with metallographic sandpaper of grades 180#, 400#, 600#, 800#, and 1600#. Then, it was polished to a mirror finish with diamond polishing paste of different grades W5 and W2.5, and then wiped with anhydrous ethanol. Finally, the single-crystal silicon and TC4 titanium alloy substrates were ultrasonically cleaned for 10 minutes and dried.

[0051] (3) Install the substrate and target material into the sample stage and sputtering source position in the vacuum chamber of the magnetron sputtering equipment, respectively.

[0052] (4) Close the vacuum chamber, turn on the chiller and vacuum gauge, and first turn on the mechanical pump to perform a rough vacuum in the vacuum chamber until the pressure reaches 2×10⁻⁶. -3 When the pressure reaches 5 Pa, the molecular pump is turned on to further evacuate the vacuum, until the vacuum reaches 5 × 10⁻⁶ Pa. -4 Pa.

[0053] (5) After vacuuming, open the sample stage valve and maintain the sample stage speed at 15 rpm. Turn on the negative bias voltage -150V to clean the substrate for 15 minutes. Keep the sputtering target baffle closed, introduce pure Ar gas, and adjust the DC power of the Ti target and TiCrSiWTaGd high-entropy alloy target to 200W and 300W respectively for pre-sputtering. The pre-sputtering time is 5 minutes to remove impurities and contaminants from the target surface.

[0054] (6) After pre-sputtering, N2 is introduced, and the flow rate ratio of Ar and N2 in the mixed gas is adjusted to 1:4. The total gas flow rate is 60 sccm, the working pressure is 0.5 Pa, the DC sputtering power of Ti target is adjusted to 200 W, the Ti sputtering target baffle is opened, and the substrate is sputtered and coated. The sputtering time is 30 min. After sputtering, a TiN transition layer can be obtained on the sample surface.

[0055] (7) Adjust the Ar:N2 mixed gas flow ratio to 3:1, the total flow rate of the Ar and N2 mixed gas is 80 sccm, the working gas pressure is 0.5 Pa, the power of the TiCrSiWTaGd high-entropy alloy target is 600 W, the TiCrSiWTaGd high-entropy alloy sputtering target baffle is opened, and the sputtering time is 240 min, depositing a TiCrSiWTaGd high-entropy alloy nitride film on the substrate surface. The molecular formula of the high-entropy alloy nitride in the two TC4 titanium alloy substrate hard films is Ti 14 Cr 13 Si 11 W 12 Ta8Gd8N 34 The FCC structure has a film thickness of 4.2 μm.

[0056] Example 3

[0057] A method for preparing a radiation-resistant high-entropy alloy nitride hard thin film, characterized by comprising the following steps:

[0058] (1) Target preparation: Pure Ti target with a purity of 99.99% and a size of 101.6 mm, prepared by vacuum melting, and TiCrSiWTaGd high-entropy alloy target with a purity of 99.99% and a size of 101.6 mm, prepared by powder metallurgy, were selected. Ti:Cr:Si:W:Ta:Gd=a':b':c':d':e':f', where a'=28, b'=26, c'=17, d'=12, e'=9, f'=8, a'+b'+c'+d'+e'+f'=100.

[0059] (2) Substrate Preparation: In this embodiment, a purchased polished single-crystal silicon (100) substrate and TC4 titanium alloy were selected. The single-crystal silicon substrate was used for morphological observation and crystal structure testing of TiCrSiWTaGd high-entropy alloy nitride thin films, while the TC4 titanium alloy substrate was used for testing the nanohardness, friction coefficient, and wear rate of the thin films. For the TC4 titanium alloy, the TC4 titanium alloy rod was first cut into two Φ40×10mm circular substrates using a wire cutting device. Then, the scratches formed by cutting were removed by sequentially polishing with metallographic sandpaper of grades 180#, 400#, 600#, 800#, and 1600#. Then, it was polished to a mirror finish with diamond polishing paste of different grades W5 and W2.5, and then wiped with anhydrous ethanol. Finally, the single-crystal silicon and TC4 titanium alloy substrates were ultrasonically cleaned for 10 minutes and dried.

[0060] (3) Install the substrate and target material into the sample stage and sputtering source position in the vacuum chamber of the magnetron sputtering equipment, respectively.

[0061] (4) Close the vacuum chamber, turn on the chiller and vacuum gauge, and first turn on the mechanical pump to perform a rough vacuum in the vacuum chamber until the pressure reaches 2×10⁻⁶. -3 When the pressure reaches 5 Pa, the molecular pump is turned on to further evacuate the vacuum, until the vacuum reaches 5 × 10⁻⁶ Pa. -4 Pa.

[0062] (5) After vacuuming, open the sample stage valve and maintain the sample stage speed at 15 rpm. Turn on the negative bias voltage -150V to clean the substrate for 15 minutes. Keep the sputtering target baffle closed, introduce pure Ar gas, and adjust the DC power of the Ti target and TiCrSiWTaGd high-entropy alloy target to 200W and 300W respectively for pre-sputtering. The pre-sputtering time is 5 minutes to remove impurities and contaminants from the target surface.

[0063] (6) Pre-sputtering After sputtering, N2 is introduced, and the flow rate ratio of Ar and N2 in the mixed gas is adjusted to 1:4. The total gas flow rate is 60 sccm, the working pressure is 0.5 Pa, the DC sputtering power of Ti target is adjusted to 200 W, the Ti sputtering target baffle is opened, and the substrate is sputtered and coated. The sputtering time is 30 min. After sputtering, a TiN transition layer can be obtained on the sample surface.

[0064] (7) Adjust the Ar:N2 mixed gas flow ratio to 1:3, the total flow rate of the Ar and N2 mixed gas to 80 sccm, the working gas pressure to 0.5 Pa, the power of the TiCrSiWTaGd high-entropy alloy target to 300 W, the TiCrSiWTaGd high-entropy alloy sputtering target baffle to be opened, and the sputtering time to 240 min, depositing a TiCrSiWTaGd high-entropy alloy nitride film on the substrate surface. The molecular formula of the high-entropy alloy nitride in the two TC4 titanium alloy substrate hard films is Ti 10 Cr8Si 11 W 10 Ta6Gd6N 49 The film has an FCC structure and a thickness of 2.7 μm.

[0065] Example 4

[0066] A method for preparing a radiation-resistant high-entropy alloy nitride hard thin film, characterized by comprising the following steps:

[0067] (1) Target preparation: Pure Ti target with a purity of 99.99% and a size of 101.6 mm, prepared by vacuum melting, and TiCrSiWTaGd high-entropy alloy target with a purity of 99.99% and a size of 101.6 mm, prepared by powder metallurgy, were selected. Ti:Cr:Si:W:Ta:Gd=a':b':c':d':e':f', where a'=28, b'=26, c'=17, d'=14, e'=8, f'=7, a'+b'+c'+d'+e'+f'=100.

[0068] (2) Substrate Preparation: In this embodiment, a purchased polished single-crystal silicon (100) substrate and TC4 titanium alloy were selected. The single-crystal silicon substrate was used for morphological observation and crystal structure testing of TiCrSiWTaGd high-entropy alloy nitride thin films, while the TC4 titanium alloy substrate was used for testing the nanohardness, friction coefficient, and wear rate of the thin films. For the TC4 titanium alloy, the TC4 titanium alloy rod was first cut into two Φ40×10mm circular substrates using a wire cutting device. Then, the scratches formed by cutting were removed by sequentially polishing with metallographic sandpaper of grades 180#, 400#, 600#, 800#, and 1600#. Then, it was polished to a mirror finish with diamond polishing paste of different grades W5 and W2.5, and then wiped with anhydrous ethanol. Finally, the single-crystal silicon and TC4 titanium alloy substrates were ultrasonically cleaned for 10 minutes and dried.

[0069] (3) Install the substrate and target material into the sample stage and sputtering source position in the vacuum chamber of the magnetron sputtering equipment, respectively.

[0070] (4) Close the vacuum chamber, turn on the chiller and vacuum gauge, and first turn on the mechanical pump to perform a rough vacuum in the vacuum chamber until the pressure reaches 2×10⁻⁶. -3 When the pressure reaches 5 Pa, the molecular pump is turned on to further evacuate the vacuum, until the vacuum reaches 5 × 10⁻⁶ Pa. -4 Pa.

[0071] (5) After vacuuming, open the sample stage valve and maintain the sample stage speed at 15 rpm. Turn on the negative bias voltage -150V to clean the substrate for 15 minutes. Keep the sputtering target baffle closed, introduce pure Ar gas, and adjust the DC power of the Ti target and TiCrSiWTaGd high-entropy alloy target to 200W and 300W respectively for pre-sputtering. The pre-sputtering time is 5 minutes to remove impurities and contaminants from the target surface.

[0072] (6) After pre-sputtering, N2 is introduced, and the flow rate ratio of Ar and N2 in the mixed gas is adjusted to 1:4. The total gas flow rate is 60 sccm, the working pressure is 0.5 Pa, the DC sputtering power of Ti target is adjusted to 200 W, the Ti sputtering target baffle is opened, and the substrate is sputtered and coated. The sputtering time is 30 min. After sputtering, a TiN transition layer can be obtained on the sample surface.

[0073] (7) Adjust the Ar:N2 mixed gas flow ratio to 1:3, the total flow rate of the Ar and N2 mixed gas to 80 sccm, the working gas pressure to 0.5 Pa, the power of the TiCrSiWTaGd high-entropy alloy target to 600 W, the TiCrSiWTaGd high-entropy alloy sputtering target baffle to be opened, and the sputtering time to 240 min, depositing a TiCrSiWTaGd high-entropy alloy nitride film on the substrate surface. The molecular formula of the high-entropy alloy nitride in the two TC4 titanium alloy substrate hard films is Ti15 Cr 14 Si 10 W 10 Ta8Gd7N 36 The FCC structure has a film thickness of 3.9 μm.

[0074] Comparative Example 1

[0075] (1) Target preparation: Pure Ti target with a purity of 99.99% and a size of 101.6 mm, prepared by vacuum melting, was selected.

[0076] (2) Substrate Preparation: In this embodiment, a purchased polished monocrystalline silicon (100) substrate and TC4 titanium alloy were selected. The monocrystalline silicon substrate was used for TiN thin film morphology observation and crystal structure testing, while the TC4 titanium alloy substrate was used for thin film nano-hardness, friction coefficient, and wear rate testing. For the TC4 titanium alloy, the TC4 titanium alloy rod was first cut into two Φ40×10mm circular substrates using a wire cutting device. Then, the scratches formed by cutting were removed by sequentially polishing with metallographic sandpaper of grades 180#, 400#, 600#, 800#, and 1600#. Then, it was polished to a mirror finish with diamond polishing paste of different grades W5 and W2.5, and then wiped with anhydrous ethanol. Finally, the monocrystalline silicon and TC4 titanium alloy substrates were ultrasonically cleaned for 10 minutes and dried.

[0077] (3) Install the substrate and target material into the sample stage and sputtering source position in the vacuum chamber of the magnetron sputtering equipment, respectively.

[0078] (4) Close the vacuum chamber, turn on the chiller and vacuum gauge, and first turn on the mechanical pump to perform a rough vacuum in the vacuum chamber until the pressure reaches 2×10⁻⁶. -3 When the pressure reaches 5 Pa, the molecular pump is turned on to further evacuate the vacuum, until the vacuum reaches 5 × 10⁻⁶ Pa. -4 Pa.

[0079] (5) After vacuuming, open the sample stage valve and keep the sample stage speed at 15 rpm. Turn on the negative bias voltage -150V to clean the substrate for 15 minutes. Keep the sputtering target baffle closed, introduce pure Ar gas, and adjust the DC power supply of the Ti target to 200W for pre-sputtering for 5 minutes to remove impurities and contaminants from the target surface.

[0080] (6) After pre-sputtering, N2 is introduced, and the flow rate ratio of Ar and N2 in the mixed gas is adjusted to 1:4. The total gas flow rate is 60 sccm, the working pressure is 0.5 Pa, the DC sputtering power of Ti target is adjusted to 350 W, the Ti sputtering target baffle is opened, and the substrate is sputtered and coated. The sputtering time is 360 min. After sputtering, TiN film can be obtained on the sample surface. The sputtered TiN film is detected to be an FCC structure, and the film thickness is 3.4 μm.

[0081] Performance testing

[0082] 1. Ionizing radiation test

[0083] use 60 Co (gamma-ray) irradiation source was used to irradiate some samples of TiCrSiWTaGd high-entropy alloy nitride hard films in Examples 1-4 and TiN film in Comparative Example 1 with a total dose of 5 × 10⁻⁶. 9 Radius (Si) irradiated with gamma rays to compare the properties of unirradiated and irradiated thin films.

[0084] 2. Properties of rigid thin films

[0085] The surface nanohardness of the TiCrSiWTaGd high-entropy alloy nitride hard films in Examples 1-4 and the TiN film in Comparative Example 1 was measured using a nanoindenter. The results are shown in Table 1, which contains data before ionization irradiation.

[0086] The friction coefficient curves and wear rates of the TiCrSiWTaGd high-entropy alloy nitride hard films in Examples 1-4 and the TiN film in Comparative Example 1 before and after irradiation were determined using a ball-and-disc friction tester. The results are shown in Table 1 and 2. Figure 2 .

[0087] Table 1 Comparison of film properties before and after ionizing radiation irradiation

[0088]

[0089] It can be seen that after the TiCrSiWTaGd high-entropy alloy nitride hard films in Examples 1-4 were irradiated by a ground-based ionization irradiation simulation device, the crystal structure remained unchanged, and the surface nano-hardness and wear resistance were almost unchanged. However, after the TiN film in Comparative Example 1 was irradiated by the ground-based ionization irradiation simulation device, the crystal structure changed from FCC to FCC+ amorphous structure. The hardness was improved due to the formation of amorphous material, but the coefficient of friction increased, the wear rate increased, and the wear resistance of the film deteriorated.

[0090] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

[0091] The contents not described in detail in this specification are common knowledge to those skilled in the art.

Claims

1. An anti-radiation high-entropy alloy nitride hard film, characterized in that, The molecular formula of the high-entropy alloy nitride in the hard film is Ti a Cr b Si c W d Ta e Gd f N x , wherein a=8-15, b=8-15, c=6-12, d=6-12, e=6-8, f=6-8, x=30-50, a+b+c+d+e+f+x=100.

2. The radiation resistant high-entropy alloy nitride hard film of claim 1, wherein, The overall thickness of the hard film is 2.5-4.5 microns, and the surface nano-hardness is not less than 30 GPa.

3. The radiation resistant high-entropy alloy nitride hard film of claim 1, wherein, When the N element content in the high-entropy alloy nitride of the hard film is x=45-50, the metal atoms and nitrogen atoms reach saturation in bonding, and the nano-hardness of the hard film reaches 50-63 GPa.

4. A method of producing the anti-radiation high-entropy alloy nitride hard film according to any one of claims 1 to 3, characterized by, The method comprises the following steps: Prepare a pure Ti target and a TiCrSiWTaGd high-entropy alloy target; Prepare a substrate and pretreat it to a plating film state; Use the Ti target to perform sputter plating on the substrate to obtain a TiN transition layer on the surface of the substrate; Use the TiCrSiWTaGd high-entropy alloy target to perform sputter plating on the TiN transition layer to obtain a high-entropy alloy nitride hard film.

5. The method of claim 4, wherein the method is characterized by: The atomic ratio of each element in the TiCrSiWTaGd high-entropy alloy target is Ti:Cr:Si:W:Ta:Gd=a':b':c':d':e':f', wherein a'=10-30, b'=10-30, c'=5-20, d'=5-15, e'=5-10, and f'=5-10, and a'+b'+c'+d'+e'+f'=100.

6. The method of claim 4, wherein the method is characterized by: The substrate is one of a titanium alloy, an aluminum alloy, an aluminum-lithium alloy, or a magnesium alloy.

7. The method of claim 4, wherein the method is characterized by: Before the step of using the Ti target to perform sputter plating on the substrate to obtain a TiN transition layer on the surface of the substrate, the method further comprises: pre-sputtering the Ti target and the TiCrSiWTaGd high-entropy alloy target to remove impurities and contaminants on the surfaces of the Ti target and the TiCrSiWTaGd high-entropy alloy target.

8. The method of claim 4, wherein the method is characterized by: The step of using the Ti target to perform sputter plating on the substrate to obtain a TiN transition layer on the surface of the substrate is implemented in the following manner: N2 is introduced into a sputter chamber of a magnetron sputtering device, the ratio of Ar and N2 gas flow in the mixed gas is adjusted to 1:3-1:5, the total gas flow is 50-80 sccm, the working gas pressure is 0.1-1.0 Pa, the direct-current sputtering power of the Ti target is adjusted to 150-250 W, sputter plating is performed on the substrate, the sputtering time is 20-40 min, and a TiN transition layer is obtained on the surface of the substrate after sputtering.

9. The method of claim 4, wherein the method is characterized by: The step of using the TiCrSiWTaGd high-entropy alloy target to perform sputter plating on the TiN transition layer to obtain a high-entropy alloy nitride hard film is implemented in the following manner: The ratio of Ar and N2 gas flow in the mixed gas is adjusted to 3:1-1:3, the total flow of the Ar and N2 mixed gas is 60-100 sccm, the direct-current sputtering power of the TiCrSiWTaGd high-entropy alloy target is then adjusted to 300-600 W to ensure that the target can glow, sputter plating is performed on the substrate, and a high-entropy alloy nitride hard film is obtained on the surface of the TiN transition layer of the substrate.

10. A radiation resistant wear resistant blanket, characterized by, The bottom layer is located between the substrate and the surface layer, and the surface layer is Ti a Cr b Si c W d Ta e Gd f N x Layer, wherein a = 8-15, b = 8-15, c = 6-12, d = 6-12, e = 6-8, f = 6-8, x = 30-50, a+b+c+d+e+f+x = 100.

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