A high temperature resistant high entropy oxide coating and its preparation method and application

Abstract

The present invention provides a high-temperature resistant high-entropy oxide coating and a preparation method and application thereof, belonging to the technical field of high-entropy alloys. After the substrate is subjected to surface ultrasonic cleaning treatment, a unit metal coating, a ternary metal coating and a high-entropy metal oxide coating are sequentially obtained by magnetic filtration cathode vacuum arc deposition, wherein the types of metal elements in the high-entropy metal oxide coating are not less than 5, and the content of each metal element is independently 8-30%. The magnetic filtration cathode vacuum arc deposition of the present invention can filter out large particles and neutral atoms generated by arcing, and the ionization rate of the deposited particles after magnetic filtration is close to 100%, thereby obtaining a pure plasma beam without large particles, and high-quality coatings can be deposited at low substrate temperatures. High-entropy metal oxides with adjustable element types and element contents are prepared by co-deposition magnetic filtration cathode vacuum arc, and the coating has high bonding strength, good compactness, and excellent high-temperature resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of high entropy alloys, and in particular to a high temperature resistant high entropy oxide coating and a preparation method and application thereof. Background Art

[0002] High temperature resistant coatings are generally prepared by physical vapor deposition methods such as magnetron sputtering, electron beam evaporation, sintering and conventional electroplating. Zirconium oxide, aluminum oxide unit metal oxides, or chromium aluminum oxide and other binary metal oxides are prepared. The advantages are simple deposition equipment and relatively good control of deposition process; but there are also corresponding disadvantages: such as relatively poor film quality, weak bonding strength, poor density, and high temperature instability. Summary of the invention

[0003] In view of this, the purpose of the present invention is to provide a high temperature resistant high entropy oxide coating and a preparation method and application thereof. The high temperature resistant high entropy oxide prepared by the present invention has high bonding strength, good compactness and good high temperature stability.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a high temperature resistant high entropy oxide coating, comprising the following steps:

[0006] After the substrate is subjected to surface ultrasonic cleaning, a unit metal coating, a ternary metal coating and a high entropy metal oxide coating are sequentially obtained by magnetic filtration cathode vacuum arc deposition. The high entropy metal oxide coating contains no less than 5 types of metal elements, and the atomic content of each metal element is independently 8 to 30%.

[0007] Preferably, the metal elements in the high entropy metal oxide coating include five or more of Ti, Cr, Co, Mo, Y, Ni, Au, Ag, Cu and Al.

[0008] Preferably, the high entropy metal oxide coating has a thickness of 1 to 10 μm.

[0009] Preferably, when forming the high entropy metal oxide, the number of cathode arcs enabled when the magnetic filtered cathode vacuum arc deposition is started is 4, and there are four arc targets. The starting current of each arc is 20-180A, and the starting voltage is 20-30V. After the arc is started, oxygen is introduced, and the oxygen intake amount changes periodically. The gas amount in one cycle is: 60-100sccm, 10-20sccm and 90-120sccm respectively. The cycle time is 5-10min, and the number of cycles is 10-20.

[0010] Preferably, the unit metal coating is a Ni metal layer, a Ti metal layer, an Ag metal layer or a Cr metal layer.

[0011] Preferably, when forming the unit metal coating, the bias power of the magnetic filtration cathode vacuum arc deposition is 0.01-1 MW, the bias pulse frequency is 10-80 Hz, and the pulse width is 1.2 ms.

[0012] Preferably, the metal elements in the ternary metal coating include any three of Ti, Al, Mo, Ni, Y, Ag and Au.

[0013] Preferably, when forming the ternary metal coating, the number of cathode arcs enabled by the magnetic filtration cathode vacuum arc deposition is 2, the arc starting current is 20-180A, and the arc starting voltage is 20-30V; when starting the arc, the two cathode arc currents are continuously and automatically adjusted, with an adjustment step of 5A, one cathode arc continuously increases from 20-80A, and the other continuously decreases from 80-20A, and the sum of the two cathode arc currents is 100A, which changes periodically.

[0014] The present invention also provides a high-temperature resistant high-entropy oxide coating obtained by the preparation method described in the above technical solution, comprising a substrate layer, a cleaning layer, a unit metal coating, a ternary metal coating and a high-entropy metal oxide coating stacked in sequence.

[0015] The present invention also provides applications of the high temperature resistant high entropy oxide coating described in the above technical solution in the fields of aerospace, electronic information and new energy.

[0016] The present invention provides a preparation method of a high-temperature resistant high-entropy oxide coating, comprising the following steps: after a substrate is subjected to surface ultrasonic cleaning treatment, a unit metal coating, a ternary metal coating and a high-entropy metal oxide coating are sequentially obtained by magnetic filtration cathode vacuum arc deposition, wherein the high-entropy metal oxide coating contains no less than 5 types of metal elements, and the content of each metal element is independently 8 to 30%.

[0017] The magnetic filtration cathode vacuum arc deposition of the present invention can filter out large particles and neutral atoms generated by arcing. The ionization rate of the deposited particles after magnetic filtration is close to 100%, and a pure plasma beam without large particles is obtained. High-quality coatings can be deposited at a low substrate temperature. High-entropy metal oxides with adjustable element types and element contents are prepared by co-deposition magnetic filtration cathode vacuum arc. The coating has high bonding strength, good density, and excellent high-temperature resistance.

[0018] Furthermore, the present invention utilizes four magnetic filtration structures coupled with a common magnetic field transport channel technology; designs a structure in which four arc source structures are mixed and uniformly drawn out, so as to achieve uniform distribution of multiple elements in the plasma and realize uniform deposition of the film layer;

[0019] Furthermore, the present invention utilizes high-power pulse bias voltage when depositing the unit metal coating to achieve deposition preparation of flexible low-stress metal;

[0020] Furthermore, when depositing the ternary metal coating, the present invention utilizes two magnetic filtration deposition arc starting currents to work in a cross-cycle manner (one changes from large to small, and the other changes from small to large), thereby achieving high-density deposition, and can naturally establish a concentration gradient of element species in a high-temperature environment, thereby inhibiting the diffusion of elements into high-entropy oxides or into the substrate, thereby improving high-temperature stability;

[0021] Furthermore, when depositing a high entropy metal oxide coating in the present invention, target poisoning easily occurs after oxygen is introduced using conventional magnetic filtration technology, thereby causing deposition interruption. The focusing coil and the mixing coil provided in the present invention can increase the driving force for oxygen ions to diffuse into the vacuum chamber, inhibit their diffusion into the target, reduce target poisoning, and improve deposition continuity.

[0022] Furthermore, the incorporation of Ti and Al into the high entropy metal oxide coating forms amorphous TiO2 and nanocrystalline Al2O3 by controlling the parameters in the preparation process. Amorphous TiO2 and nanocrystalline Al2O3 can effectively block the diffusion of oxygen at high temperatures and improve high temperature stability.

[0023] The present invention also provides a high-temperature resistant high-entropy oxide coating prepared by the preparation method described in the above technical scheme. The high-temperature resistant high-entropy oxide coating of the present invention has high bonding strength and good density. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 1 is a schematic diagram of the structure of the high temperature resistant high entropy oxide coating of the present invention, wherein 101 is a substrate layer, 102 is a cleaning layer, 103 is a unit metal coating, 104 is a ternary metal coating, and 105 is a high entropy metal oxide coating;

[0025] Figure 2 Schematic diagram of the structure of the device for performing the magnetic filtration cathode vacuum arc deposition of the present invention, wherein 201 is an air inlet, 202 is a negative pressure inlet for a workpiece, 203 is a mixing coil, 204 is a focusing coil, 205 is a No. 1 cathode arc target, 206 is a No. 2 cathode arc target, 207 is a No. 3 cathode arc target, 208 is a No. 4 cathode arc target, 209 is an extraction plasma, and 210 is a vacuum chamber;

[0026] Figure 3 is the bonding strength curve of the coating of Examples 1 to 4 at room temperature;

[0027] Figure 4 The bonding strength curves of the coatings of Examples 1 to 4 after being treated at 600° C. for 1 hour;

[0028] Figure 5 The present invention provides a flow chart for preparing a high temperature resistant high entropy oxide coating. DETAILED DESCRIPTION

[0029] The present invention provides a method for preparing a high temperature resistant high entropy oxide coating, comprising the following steps:

[0030] After the substrate is subjected to surface ultrasonic cleaning treatment, a unit metal coating, a ternary metal coating and a high entropy metal oxide coating are successively obtained by magnetic filtration cathode vacuum arc deposition (magnetic filtration technology). The high entropy metal oxide coating contains no less than 5 types of metal elements, and the atomic content of each metal element is independently 8 to 30%.

[0031] The present invention performs ultrasonic cleaning treatment on the surface of the substrate.

[0032] In the present invention, the material of the substrate is preferably stainless steel, high-speed steel, titanium alloy, zirconium alloy, or magnesium alloy.

[0033] In the present invention, the ultrasonic cleaning treatment is used to remove oil, impurities and the like on the surface of the material, and preferably includes the following steps: ultrasonic cleaning is performed in acetone, ethanol and deionized water in sequence, the frequency of the ultrasonic cleaning treatment is preferably 20 to 90 Hz, the time is preferably 10 to 60 min, and the temperature is preferably room temperature to 50°C.

[0034] In the present invention, the metal elements in the high entropy metal oxide coating preferably include five or more of Ti, Cr, Co, Mo, Y, Ni, Au, Ag, Cu and Al, and more preferably Ti-Y-Ni-Au-Al, Ti-Y-Ni-Ag-Al, Ti-Y-Cr-Au-Al, Ti-Y-Cr-Ag-Al, Ti-Y-Ni-Au-Al-Mo, Ti-Y-Ni-Ag-Al-Mo, Ti-Y-Cr-Au-Al-Mo or Ti-Y-Cr-Ag-Al-Mo.

[0035] In the present invention, the thickness of the high entropy metal oxide coating is preferably 1 to 10 μm, more preferably 5 to 10 μm.

[0036] In the present invention, the high entropy metal oxide coating is an amorphous phase encapsulating nanocrystals, wherein titanium dioxide and aluminum oxide are an amorphous non-crystalline phase, and other metal oxides are nanocrystals.

[0037] In the present invention, when forming the high entropy metal oxide, the number of cathode arcs enabled when the magnetic filtered cathode vacuum arc deposition is started is preferably 4, and the arc targets are preferably four. The starting current of each arc is preferably 20-180A, and the starting voltage is preferably 20-30V. After the arc is started, oxygen is preferably introduced, and the intake amount of the oxygen is preferably changed periodically. The gas volume in one cycle is preferably: 60-100sccm, 10-20sccm and 90-120sccm, respectively. The cycle time is preferably 5-10min, and the number of cycles is preferably 10-20.

[0038] In the present invention, when forming the high entropy metal oxide, the negative pressure of the magnetic filtration cathode vacuum arc deposition is preferably 10 to 50 KV, and the duty cycle is preferably 1 to 4%.

[0039] In the present invention, the unit metal coating is preferably a Ni metal layer, a Ti metal layer, an Ag metal layer or a Cr metal layer.

[0040] In the present invention, the thickness of the unit metal coating is preferably 100 to 200 nm, more preferably 140 to 160 nm.

[0041] In the present invention, the deposited metal phase of the unit metal coating is preferably an amorphous phase, and the film layer folding toughness is greater than 5000 times without cracking; the unit metal coating is a strong and tough metal element, and the internal phase structure is an amorphous phase when the thickness is 10 to 200 nm. Cracking mainly occurs at the grain boundaries. The amorphous phase can greatly reduce the growth and spread of cracks.

[0042] In the present invention, when forming the unit metal coating, the bias power of the magnetic filtration cathode vacuum arc deposition is preferably 0.01-1MW, the bias pulse frequency is preferably 10-80Hz, the pulse width is preferably 1.2ms, and the bias can accelerate ions to an energy of 50-120KeV during deposition; the negative pressure is preferably 800V, and the duty cycle is preferably 20-50%.

[0043] In the present invention, the metals in the ternary metal coating preferably include any three of Ti, Al, Mo, Ni, Y, Ag and Au.

[0044] In the present invention, the thickness of the ternary metal coating is preferably 500-2000 nm, more preferably 1000-1500 nm.

[0045] In the present invention, the deposited metal phase of the ternary metal coating is preferably an amorphous phase, without alloy phase generation, and the film layer has a folding toughness greater than 5000 times without cracking.

[0046] In the present invention, when forming the ternary metal coating, the number of cathode arcs enabled by the magnetic filtration cathode vacuum arc deposition is preferably 2, the arc starting current is preferably 20-180A, and the arc starting voltage is preferably 20-30V; when starting the arc, the two cathode arc currents are preferably continuously and automatically adjusted, and the adjustment step is preferably 5A, one cathode arc is preferably continuously increased from 20-80A, and the other is preferably continuously reduced from 80-20A, and the sum of the two cathode arc currents is 100A, which changes periodically; the negative pressure is preferably 10-50kV, and the duty cycle is preferably 5-10%.

[0047] In the present invention, the negative pressure when forming the ternary metal coating is preferably higher than the negative pressure when forming the unit metal coating, which can overcome the disadvantage that Ti, Al and the like are not as tough as gold or silver, and can produce a strong thermal peak effect in the micro-region, thereby greatly increasing their toughness.

[0048] Figure 2 This is a schematic diagram of the device structure for performing the magnetic filtration cathode vacuum arc deposition of the present invention, wherein 201 is an air inlet, 202 is a negative pressure inlet for a workpiece, 203 is a mixing coil, 204 is a focusing coil, 205 is cathode arc target No. 1, 206 is cathode arc target No. 2, 207 is cathode arc target No. 3, 208 is cathode arc target No. 4, 209 is an induced plasma, and 210 is a vacuum chamber.

[0049] In a specific embodiment of the present invention, when forming the high temperature resistant high entropy oxide coating, the parameters of the magnetic filtration cathode vacuum arc deposition preferably include:

[0050] No. 1 cathode arc target is an alloy target, which is TiAl, TiMo, and the arc starting current is 20-50A;

[0051] No. 2 cathode arc target is a precious metal target, Ag or Au target, and the arc starting current is 30~60A;

[0052] No. 3 cathode arc target is an alloy target, NiY or CrY target, and the arc starting current is 100~180A;

[0053] No. 4 cathode arc target is a rare earth element target, Y target, and the arc starting current is 120~160A;

[0054] When depositing the high entropy metal oxide coating, the parameters of the oxygen at different flow rates are as follows:

[0055] 1) At 60-100 sccm gas volume:

[0056] No. 1 cathode arc target is an alloy target with an arc starting current of 40-50A;

[0057] No. 2 cathode arc target is a precious metal target with an arc starting current of 50-60A;

[0058] No. 3 cathode arc target is an alloy target with an arc starting current of 100-110A;

[0059] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0060] In this process, the content of amorphous titanium oxide or aluminum oxide is 50wt% to 80wt%, which helps to inhibit crack propagation in high temperature environment;

[0061] 2) At 10-20 sccm gas volume:

[0062] No. 1 cathode arc target is an alloy target with an arc starting current of 50A;

[0063] No. 2 cathode arc target is a precious metal target with an arc starting current of 60A;

[0064] No. 3 cathode arc target is an alloy target with an arc starting current of 0A;

[0065] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0066] In this process, a small amount of aluminum oxide or titanium oxide is formed, with a content of 10wt% to 30wt% and a metal phase of 40wt% to 80wt%, which helps to release internal stress at high temperatures;

[0067] 3) At 90-120 sccm gas volume:

[0068] No. 1 cathode arc target is an alloy target with an arc starting current of 30A;

[0069] No. 2 cathode arc target is a precious metal target with an arc starting current of 40A;

[0070] No. 3 cathode arc target is an alloy target with an arc starting current of 130-180A;

[0071] No. 4 cathode arc target is a rare earth element target with an arc starting current of 120 to 160A;

[0072] In this process, a high entropy metal oxide coating of five or more metals is formed. The oxide uses rare earth metal oxides as solutes and transition metal oxides as solvents, which are fully mixed to achieve mutual inhibition of growth of metal oxides at high temperatures, thereby improving high temperature stability.

[0073] In the present invention, the magnetic filtration cathode vacuum arc deposition is a high ionization rate technology with good controllability of the film deposition process and greatly improved film properties (including film-base bonding, mechanical properties, friction and wear resistance, and chemical corrosion resistance). The present invention combines multiple vacuum cathode arc deposition systems, changes the spatial layout and potential distribution of the vacuum chamber, and increases the plasma density, thereby achieving controllable number of element types and element content of the high entropy oxide alloy coating to a certain extent.

[0074] In the present invention, the frequency of the focusing coil 204 is preferably 0-1KHz, and the current is preferably 0-200A; the frequency of the mixing coil 203 is preferably 0-200Hz, and the current is preferably 1-10KA. The magnetic induction intensity generated in the mixing coil 203 is preferably 1-800mT, and metal ions can be strongly mixed under the action of the Lorentz force under the action of the magnetic field. Under the action of the strong magnetic field, the spiral radius of the electrons in the plasma is 1-10μm, and the collision with the oxygen introduced can achieve full ionization of oxygen, and the ionization degree is greater than 80%, which is convenient for forming oxide nanocrystals in the film forming process.

[0075] In the present invention, when depositing the high entropy metal oxide coating, the angle between each magnetic filtration lead-out system and the normal of the workpiece is preferably 20-30°, the magnetic fields in the outlet directions of the four lead-out systems are N, S, N, S respectively, and the magnetic fields of two adjacent outlets are opposite. When used simultaneously, plasma mixing is performed at the lead-out port, and the plasma concentration is preferably 20%-50%, which is greater than that of the magnetic filtration system used alone. The deposition rate of the overall film layer is preferably 3μm / h-10μm / h.

[0076] In the present invention, the magnetic fields N and S are preferably realized by the direction of the coil current.

[0077] Figure 5 The present invention provides a flow chart for preparing a high temperature resistant high entropy oxide coating.

[0078] The present invention also provides a high-temperature resistant high-entropy oxide coating obtained by the preparation method described in the above technical solution, comprising a substrate layer, a cleaning layer, a unit metal coating, a ternary metal coating and a high-entropy metal oxide coating stacked in sequence.

[0079] In the present invention, the hardness of the high-temperature resistant high-entropy oxide coating is preferably 20 to 35 GPa, the internal stress is preferably 0.5 to 3 GPa, and the bonding strength of the oxide layer coating at a temperature of 600°C is preferably 60 to 100N.

[0080] Figure 1 Schematic diagram of the structure of the high temperature resistant high entropy oxide coating of the present invention, wherein 101 is a substrate layer, 102 is a cleaning layer, 103 is a unit metal coating, 104 is a ternary metal coating, and 105 is a high entropy metal oxide coating.

[0081] The present invention also provides applications of the high temperature resistant high entropy oxide coating described in the above technical solution in the fields of aerospace, electronic information and new energy.

[0082] In order to further illustrate the present invention, the high temperature resistant high entropy oxide coating provided by the present invention and its preparation method and application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present invention.

[0083] Example 1

[0084] S01 Ultrasonic cleaning of 304 stainless steel samples

[0085] S02 deposits unit metal coating based on magnetic filtration technology, with a deposition thickness of 0nm

[0086] S03 uses high-power pulse bias to deposit ternary metal coatings with a deposition thickness of 0μm;

[0087] S04 uses high-power pulse bias to deposit high entropy coatings with a deposition thickness of 5μm;

[0088] No. 1 cathode arc target is an alloy target, which is a TiAl target (atomic ratio 50%:50%);

[0089] No. 2 cathode arc target is a noble metal target, Ag target;

[0090] No. 3 cathode arc target is an alloy target, NiY target (atomic ratio 50%:50%);

[0091] No. 4 cathode arc target is a transition metal element target, Mo target;

[0092] When depositing the high entropy metal oxide coating, the oxygen intake volume changes periodically, and the gas volume in one cycle is: 60, 10, 90sccm, the cycle time is 8min, and the number of cycles is 10; the high-power pulse bias negative pressure is 3kV, the bias pulse frequency is 60Hz, and the pulse width is 1.2ms.

[0093] 1) 60sccm gas volume:

[0094] No. 1 cathode arc target is an alloy target with an arc starting current of 45A;

[0095] No. 2 cathode arc target is a precious metal target with an arc starting current of 55A;

[0096] No. 3 cathode arc target is an alloy target with an arc starting current of 100A;

[0097] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0098] 2) 10sccm gas volume:

[0099] No. 1 cathode arc target is an alloy target with an arc starting current of 50A;

[0100] No. 2 cathode arc target is a precious metal target with an arc starting current of 60A;

[0101] No. 3 cathode arc target is an alloy target with an arc starting current of 0A;

[0102] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0103] 3) 90sccm gas volume:

[0104] No. 1 cathode arc target is an alloy target with an arc starting current of 30A;

[0105] No. 2 cathode arc target is a precious metal target with an arc starting current of 40A;

[0106] No. 3 cathode arc target is an alloy target with an arc starting current of 130A;

[0107] No. 4 cathode arc target is a rare earth element target with an arc starting current of 120A;

[0108] Example 2

[0109] S01 Ultrasonic cleaning of 304 stainless steel samples

[0110] S02 deposits unit metal coating based on magnetic filtration technology, with a deposition thickness of 0nm

[0111] S03 uses high-power pulse bias to deposit ternary metal coatings with a deposition thickness of 1μm;

[0112] The metals are Ti, Al and Mo, and TiAl targets (atomic ratio 50%:50%) and Mo targets are used; two cathode arcs are enabled, the arc starting current is 50A, and the arc starting voltage is 25V; when arcing, the two cathode arc currents are continuously and automatically adjusted, and the adjustment step is 5A, from 20 to 80A, one cathode arc continuously increases from 20 to 80A, and the other continuously decreases from 80 to 20A, and the sum of the two cathode arc currents is 100A; the ternary metal layer prepared by this method has strong toughness and excellent film density; the high-power pulse bias negative voltage is 3kV, the bias pulse frequency is 60Hz, and the pulse width is 1.2ms.

[0113] S04 uses high-power pulse bias to deposit high entropy coatings with a deposition thickness of 5μm;

[0114] No. 1 cathode arc target is an alloy target, which is a TiAl target (atomic ratio 50%:50%);

[0115] No. 2 cathode arc target is a noble metal target, Ag target;

[0116] No. 3 cathode arc target is an alloy target, NiY target (atomic ratio 50%:50%);

[0117] No. 4 cathode arc target is a rare earth element target, Mo target;

[0118] When depositing the high entropy metal oxide coating, the oxygen intake volume changes periodically, and the gas volume in one cycle is: 60sccm, 10sccm, 90sccm, the cycle time is 8min, and the number of cycles is 10; the high-power pulse bias negative pressure is 3kV, the bias pulse frequency is 60Hz, and the pulse width is 1.2ms.

[0119] 1) 60sccm gas volume:

[0120] No. 1 cathode arc target is an alloy target with an arc starting current of 45A;

[0121] No. 2 cathode arc target is a precious metal target with an arc starting current of 55A;

[0122] No. 3 cathode arc target is an alloy target with an arc starting current of 100A;

[0123] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0124] 2) 10sccm gas volume:

[0125] No. 1 cathode arc target is an alloy target with an arc starting current of 50A;

[0126] No. 2 cathode arc target is a precious metal target with an arc starting current of 60A;

[0127] No. 3 cathode arc target is an alloy target with an arc starting current of 0A;

[0128] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0129] 3) 90sccm gas volume:

[0130] No. 1 cathode arc target is an alloy target with an arc starting current of 30A;

[0131] No. 2 cathode arc target is a precious metal target with an arc starting current of 40A;

[0132] No. 3 cathode arc target is an alloy target with an arc starting current of 130A;

[0133] No. 4 cathode arc target is a rare earth element target with an arc starting current of 120A;

[0134] Example 3

[0135] S01 Ultrasonic cleaning of 304 stainless steel samples

[0136] S02 deposits unit metal coating based on magnetic filtration technology with a deposition thickness of 50nm;

[0137] High-power pulse bias metal single metal deposition was used. The metal was Ag metal. The negative pressure during deposition was 3kV, the bias pulse frequency was 60Hz, and the pulse width was 1.2ms.

[0138] S03 uses high-power pulse bias to deposit ternary metal coatings with a deposition thickness of 1μm;

[0139] The metals are Ti, Al and Mo, and TiAl targets (atomic ratio 50%:50%) and Mo targets are used; two cathode arcs are enabled, the arc starting current is 50A, and the arc starting voltage is 25V; when arcing, the two cathode arc currents are continuously and automatically adjusted, and the adjustment step is 5A, from 20 to 80A, one cathode arc continuously increases from 20 to 80A, and the other continuously decreases from 80 to 20A, and the sum of the two cathode arc currents is 100A; the ternary metal layer prepared by this method has strong toughness and excellent film density; the high-power pulse bias negative voltage is 3kV, the bias pulse frequency is 60Hz, and the pulse width is 1.2ms.

[0140] S04 uses high-power pulse bias to deposit high entropy coatings with a deposition thickness of 5μm;

[0141] No. 1 cathode arc target is an alloy target, which is a TiAl target (atomic ratio 50%:50%);

[0142] No. 2 cathode arc target is a noble metal target, Ag target;

[0143] No. 3 cathode arc target is an alloy target, NiY target (atomic ratio 50%:50%);

[0144] No. 4 cathode arc target is a rare earth element target, Mo target;

[0145] When depositing the high entropy metal oxide coating, the oxygen intake volume changes periodically. The gas volume in one cycle is: 60sccm, 10sccm, 90sccm, the cycle time is 8min, and the number of cycles is 10.

[0146] 1) 60sccm gas volume:

[0147] No. 1 cathode arc target is an alloy target with an arc starting current of 45A;

[0148] No. 2 cathode arc target is a precious metal target with an arc starting current of 55A;

[0149] No. 3 cathode arc target is an alloy target with an arc starting current of 100A;

[0150] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0151] 2) 10sccm gas volume:

[0152] No. 1 cathode arc target is an alloy target with an arc starting current of 50A;

[0153] No. 2 cathode arc target is a precious metal target with an arc starting current of 60A;

[0154] No. 3 cathode arc target is an alloy target with an arc starting current of 0A;

[0155] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0156] 3) 90sccm gas volume:

[0157] No. 1 cathode arc target is an alloy target with an arc starting current of 30A;

[0158] No. 2 cathode arc target is a precious metal target with an arc starting current of 40A;

[0159] No. 3 cathode arc target is an alloy target with an arc starting current of 130A;

[0160] No. 4 cathode arc target is a rare earth element target with an arc starting current of 120A;

[0161] Example 4

[0162] S01 Ultrasonic cleaning of 304 stainless steel samples

[0163] S02 deposits unit metal coating based on magnetic filtration technology with a deposition thickness of 50nm;

[0164] High-power pulse bias metal single metal deposition was used. The metal was Ag metal. The negative pressure during deposition was 3kV, the bias pulse frequency was 60Hz, and the pulse width was 1.2ms.

[0165] S03 uses high-power pulse bias to deposit ternary metal coatings with a deposition thickness of 1μm;

[0166] The metals are Ti, Al and Mo, and TiAl targets (atomic ratio 50%:50%) and Mo targets are used; two cathode arcs are enabled, the arc starting current is 50A, and the arc starting voltage is 25V; when arcing, the currents of the two cathode arcs are continuously and automatically adjusted, with an adjustment step of 5A, from 20-80A, one cathode arc continuously increases from 20 to 80A, and the other continuously decreases from 80 to 20A, and the sum of the two cathode arc currents is 100A.

[0167] S04 uses high-power pulse bias to deposit high-entropy coatings with a deposition thickness of 10μm;

[0168] No. 1 cathode arc target is an alloy target, which is a TiAl target (atomic ratio 50%:50%);

[0169] No. 2 cathode arc target is a noble metal target, Ag target;

[0170] No. 3 cathode arc target is an alloy target, NiY target (atomic ratio 50%:50%);

[0171] No. 4 cathode arc target is a rare earth element target, Mo target;

[0172] When depositing the high entropy oxide coating, the oxygen intake volume changes periodically, and the gas volume in one cycle is: 60sccm, 10sccm, 90sccm, the cycle time is 8min, and the number of cycles is 20; the high-power pulse bias negative pressure is 3kV, the bias pulse frequency is 60Hz, and the pulse width is 1.2ms.

[0173] 1) 60sccm gas volume:

[0174] No. 1 cathode arc target is an alloy target with an arc starting current of 45A;

[0175] No. 2 cathode arc target is a precious metal target with an arc starting current of 55A;

[0176] No. 3 cathode arc target is an alloy target with an arc starting current of 100A;

[0177] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0178] 2) 10sccm gas volume:

[0179] No. 1 cathode arc target is an alloy target with an arc starting current of 50A;

[0180] No. 2 cathode arc target is a precious metal target with an arc starting current of 60A;

[0181] No. 3 cathode arc target is an alloy target with an arc starting current of 0A;

[0182] No. 4 cathode arc target is a rare earth element target with an arc starting current of 0A;

[0183] 3) 90sccm gas volume:

[0184] No. 1 cathode arc target is an alloy target with an arc starting current of 30A;

[0185] No. 2 cathode arc target is a precious metal target with an arc starting current of 40A;

[0186] No. 3 cathode arc target is an alloy target with an arc starting current of 130A;

[0187] No. 4 cathode arc target is a rare earth element target with an arc starting current of 120A.

[0188] Figure 3 : The bonding strength curves of the coatings of Examples 1 to 4 at room temperature are based on GB / T30707-2014. The room temperature bonding strengths of the coatings of Examples 1 to 4 are 11, 38, 84 and 100 N, respectively, indicating that the deposition of the unit metal layer and the deposition of the ternary metal layer as a transition layer of the high entropy alloy oxide can effectively improve the bonding strength with the substrate. In addition, the gradient deposition of the unit metal layer and the ternary metal layer has better bonding strength than the direct deposition of the ternary metal layer transition layer.

[0189] Figure 4This is the bonding strength curve of the coatings of Examples 1 to 4 after being treated at 600°C for 1 hour. The test standard is GB / T30707-2014. The high-temperature bonding strengths of Examples 1 and 2 are both below 3N, and the high-temperature bonding strengths of Examples 3 and 4 are 34 and 75N, respectively. This indicates that the samples without unit metal or unit or ternary metal transition layers have basically failed in interface bonding and greatly reduced bonding strength due to factors such as oxidation at high temperatures. The samples with unit or ternary metal transition layers have a certain ability to resist high-temperature oxidation. However, the samples with a thick high-entropy alloy oxide layer have a stronger ability to resist high-temperature oxidation, so the bonding strength is less reduced.

[0190] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a high temperature resistant high entropy oxide coating, characterized in that: The following steps are involved: After the substrate is subjected to surface ultrasonic cleaning treatment, a unit metal coating, a ternary metal coating and a high entropy metal oxide coating are sequentially obtained by magnetic filtration cathode vacuum arc deposition, wherein the atomic content of each metal element in the high entropy metal oxide coating is independently 8-30%; the thickness of the high entropy metal oxide coating is 1-10 μm; the unit metal coating is a Ni metal layer, a Ti metal layer, an Ag metal layer or a Cr metal layer; the metal elements in the ternary metal coating include any three of Ti, Al, Mo, Ni, Y, Ag and Au; the metal elements in the high entropy metal oxide coating are Ti-Y-Ni-Au-Al, Ti-Y-Ni-Ag-Al, Ti-Y-Cr-Au-Al, Ti-Y-Cr-Ag-Al, Ti-Y-Ni-Au-Al-Mo, Ti-Y-Ni-Ag-Al-Mo, Ti-Y-Cr-Au-Al-Mo or Ti-Y-Cr-Ag-Al-Mo; When forming the high entropy metal oxide, the number of cathode arcs activated during arc starting of magnetic filtration cathode vacuum arc deposition is 4, the number of arc targets is 4, the arc starting current of each is 20-180A, and the arc starting voltage is 20-30V; oxygen is introduced after arc starting, and the oxygen intake volume is periodically changed, and the gas volume in one cycle is: 60-100sccm, 10-20sccm and 90-120sccm, one cycle time is 5-10min, and the number of cycles is 10-20; When forming the ternary metal coating, the number of cathode arcs enabled by the magnetic filtration cathode vacuum arc deposition is 2, the arc starting current is 20-180A, and the arc starting voltage is 20-30V; when starting the arc, the two cathode arc currents are continuously and automatically adjusted, the adjustment step is 5A, one cathode arc continuously increases from 20-80A, and the other continuously decreases from 80-20A. The sum of the two cathode arc currents is 100A, which changes periodically.

2. The preparation method according to claim 1, characterized in that: When forming the unit metal coating, the bias power of the magnetic filtration cathode vacuum arc deposition is 0.01-1MW, the bias pulse frequency is 10-80Hz, and the pulse width is 1.2ms.

3. The high temperature resistant high entropy oxide coating obtained by the preparation method according to claim 1 or 2, characterized in that: The invention comprises a base layer, a cleaning layer, a unit metal coating, a ternary metal coating and a high entropy metal oxide coating which are stacked in sequence.

4. Application of the high temperature resistant high entropy oxide coating according to claim 3 in the fields of aerospace, electronic information and new energy.

Images