High-entropy alloy coating, atomic-scale manufacturing method of high-entropy alloy coating and application of high-entropy alloy coating in field of hydrogen energy

Abstract

The invention belongs to the technical field of hydrogen-resistant coatings, and particularly relates to a high-entropy alloy coating, an atomic-scale manufacturing method of the high-entropy alloy coating and application of the high-entropy alloy coating in the field of hydrogen energy. Compared with the prior art, the high-entropy alloy coating containing multiple metal elements is adopted to trigger the lattice distortion effect, the hydrogen diffusion resistance is remarkably increased, the amorphous / nanocrystalline structure of the high-entropy alloy coating can eliminate the grain boundary defect and block the hydrogen permeation path, and the hydrogen resistance efficiency is improved by 1-2 orders of magnitude compared with that of a traditional coating; meanwhile, due to the high mixed entropy characteristic, the composite material has the multifunctional characteristics of excellent high-temperature stability, strong interface bonding force, radiation resistance / corrosion resistance and the like; moreover, by combining advanced processes such as multi-arc magnetic filter cathode deposition (FCVA), the ultra-compact and low-defect HEA coating can be prepared at low temperature, high hydrogen resistance, mechanical strength and long-acting service reliability are considered, and a breakthrough solution is provided for extreme environments such as nuclear reactor jackets and aerospace hydrogen storage systems.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen barrier coating technology, and particularly relates to a high-entropy alloy coating, its atomic-level manufacturing method, and its application in the field of hydrogen energy. Background Technology

[0002] With the development of nuclear energy, hydrogen energy, and chemical engineering, hydrogen permeation has increasingly become a key challenge restricting the reliability and safety of materials. In high-temperature, high-pressure, or corrosive environments, hydrogen atoms easily diffuse through grain boundaries or defects in metallic materials (such as pipes, reactor cladding, and hydrogen storage containers), leading to hydrogen embrittlement, degradation of material mechanical properties, and even failure. Traditional solutions involve using specific materials, such as austenitic stainless steel and nickel-based alloys, which, while possessing some hydrogen barrier capabilities, are costly, complex to process, and difficult to meet the long-term protection requirements under extreme conditions. Hydrogen barrier coating technology, through surface engineering, deposits dense, chemically stable thin films (such as oxide, nitride, or ceramic-based coatings) on the substrate surface. Utilizing their low hydrogen diffusion coefficient and high hydrogen dissolution barrier, these films block the hydrogen atom permeation pathway, becoming the most effective method to reduce hydrogen damage and hydrogen embrittlement.

[0003] Early coating preparation technologies, such as thermal spraying and electroplating, suffer from problems such as weak adhesion, high porosity, and easy peeling at high temperatures. However, advancements in physical vapor deposition (PVD) and chemical vapor deposition (CVD) technologies have provided new ideas for the development of high-performance hydrogen barrier coatings.

[0004] Huang et al. successfully prepared a FeAl / Al2O3 composite tritium-blocking coating on the surface of 316L stainless steel using an embedding method combined with in-situ thermal oxidation. Aluminum and iron atoms in the steel substrate diffuse into each other on the steel surface, forming a FeAl alloy transition layer. Then, combined with in-situ thermal oxidation, the surface of the transition layer is selectively oxidized to form an Al2O3 film. The sample surface consists of a FeAl diffusion layer with a self-healing mechanism and an α-Al2O3 layer with excellent tritium-blocking properties (Surface & Coatings Technology 383(2020) 125282).

[0005] Liu et al. used FCVD for ion bombardment during magnetron sputtering deposition of dense CrN coatings to reduce intergranular gap formation. The density of the CrN coating was improved by disrupting grain growth through high-energy ion bombardment (Surface & Coatings Technology 437 (2022) 128326).

[0006] Zhang et al. proposed that aluminum phosphate sealing improves the deuterium permeation resistance of α-Al2O3 coatings prepared by the MOD method. The α-Al2O3 coating prepared by the organometallic decomposition method was sealed with aluminum phosphate binder. The main phases in the sealing coating are α-Al2O3 and orthophosphate AlPO4. The aluminum phosphate binder exhibits good permeability in the coating, effectively filling defects such as pores and cracks in the α-Al2O3 coating (Surface & Coatings Technology 419 (2021) 127298).

[0007] However, the aforementioned hydrogen barrier coatings still face bottlenecks such as a single material system (e.g., traditional oxides / nitrides), weak interfacial bonding, hydrogen permeation channels caused by microscopic defects (pores, grain boundaries), and high-temperature phase transition failure, making it difficult to meet the requirements of extreme working conditions such as nuclear energy and hydrogen storage and transportation. Summary of the Invention

[0008] In view of this, the technical problem to be solved by the present invention is to provide a high-entropy alloy coating that takes into account high hydrogen resistance, mechanical strength and long-term service reliability, as well as its atomic-level manufacturing method and its application in the field of hydrogen energy.

[0009] This invention provides a method for preparing a high-entropy alloy coating, comprising the following steps:

[0010] S) A high-entropy alloy coating is deposited on the substrate surface using a magnetically filtered cathode vacuum arc deposition method; the target materials used in the magnetically filtered cathode vacuum arc deposition include nickel-chromium alloy targets, titanium targets, aluminum targets and vanadium targets; the nickel content in the nickel-chromium alloy target is 20~30 wt%.

[0011] Preferably, the working gas pressure of the magnetically filtered cathode vacuum arc deposition is 0.03~2 Pa;

[0012] And / or, the magnetic filtering current intensity of the magnetic filtering cathode vacuum arc deposition is 1~2 A;

[0013] And / or, the negative bias voltage of the magnetically filtered cathode vacuum arc deposition is less than -80V or greater than or equal to -150V;

[0014] And / or, the duty cycle of the magnetically filtered cathode vacuum arc deposition is greater than or equal to 50%.

[0015] Preferably, the negative bias voltage of the magnetic filter cathode vacuum arc deposition is less than or equal to -50V or is -180V to -220V;

[0016] And / or, the duty cycle of the magnetically filtered cathode vacuum arc deposition is 90%.

[0017] Preferably, the power of each of the nickel-chromium alloy target, titanium target, aluminum target and vanadium target is 2~2.5 kW.

[0018] And / or, the time for vacuum arc deposition of the magnetically filtered cathode is 30~240 min.

[0019] Preferably, step S) specifically comprises:

[0020] S1) Pre-treatment of the substrate; the pre-treatment includes grinding and polishing and ion cleaning;

[0021] S2) A high-entropy alloy coating is deposited on the pretreated substrate surface using a magnetically filtered cathode vacuum arc deposition method.

[0022] Preferably, the grinding and polishing includes coarse grinding, medium grinding, fine grinding and fine polishing performed sequentially; the coarse grinding is performed using a 200-600 mesh grinding disc; the medium grinding is performed using an 800-1200 mesh grinding disc; the fine grinding is performed using a 1400-1600 mesh grinding disc; and the fine polishing is performed using 0.5-3 μm polishing powder and polishing cloth.

[0023] And / or, the ion cleaning is performed using an inert gas; the flow rate of the inert gas is 50~200 sccm; the working gas pressure of the ion cleaning is 0.01~0.1 Pa; the current intensity of the ion cleaning is 80~150 A; the ion cleaning is performed using a gradient decreasing negative bias voltage.

[0024] Preferably, the number of gradients of the negative bias voltage for gradient reduction is 4, specifically -850V~-750V, -650V~-550V, -450V~-350V and -250V~-150V;

[0025] The ion cleaning time is 4~12 min.

[0026] The present invention also provides a high-entropy alloy coating prepared by the above preparation method, wherein the high-entropy alloy coating comprises the metallic elements nickel, chromium, titanium, aluminum and vanadium;

[0027] The high-entropy alloy coating is an amorphous high-entropy alloy coating.

[0028] Preferably, the steady-state hydrogen permeation current of the high-entropy alloy coating is less than 5 µA·cm. -2 .

[0029] The present invention also provides an apparatus for the field of hydrogen energy, comprising the above-described high-entropy alloy coating.

[0030] This invention provides a method for preparing a high-entropy alloy coating, comprising the following steps: S) depositing a high-entropy alloy coating on a substrate surface using a magnetically filtered cathode vacuum arc deposition (FCVA) method; the target material used in the FCVA includes a nickel-chromium alloy target, a titanium target, an aluminum target, and a vanadium target; the nickel content in the nickel-chromium alloy target is 20-30 wt%. Compared with the prior art, this invention significantly increases hydrogen diffusion resistance by inducing lattice distortion effect through the use of a high-entropy alloy coating containing multiple metal elements. Its amorphous / nanocrystalline structure can eliminate grain boundary defects and block hydrogen permeation paths, improving hydrogen barrier efficiency by 1-2 orders of magnitude compared to traditional coatings. Simultaneously, the high mixing entropy characteristics endow it with excellent high-temperature stability, strong interfacial adhesion, and multifunctional properties such as radiation resistance and corrosion resistance. Furthermore, combined with advanced processes such as multi-arc magnetically filtered cathode deposition (FCVA), ultra-dense, low-defect HEA coatings can be prepared at low temperatures, balancing high hydrogen barrier performance, mechanical strength, and long-term service reliability, providing a breakthrough solution for extreme environments such as nuclear reactor cladding and aerospace hydrogen storage systems. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the four-arc head magnetically filtered cathode vacuum arc (Co-FVCA) device used in the embodiments of the present invention;

[0032] Figure 2 X-ray images of the high-entropy alloy hydrogen-barrier coatings obtained in Examples 1-4 of this invention;

[0033] Figure 3 The images show the HRTEM images of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1 and 2 of this invention, and the corresponding selected area electron diffraction patterns.

[0034] Figure 4 These are scanning electron microscope (SEM) images of the cross-sections of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1-4 of this invention.

[0035] Figure 5 This is a diagram of the apparatus for electrochemical hydrogen barrier testing of the high-entropy alloy hydrogen barrier coating obtained in Examples 1-4 of this invention;

[0036] Figure 6 The hydrogen permeation curves of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1-4 of this invention are shown.

[0037] Figure 7 The graphs show the potentiodynamic polarization curves of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1-4 of this invention in a 3.5 wt.% NaCl solution. Detailed Implementation

[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0039] Current hydrogen barrier coatings face bottlenecks such as a single material system (e.g., traditional oxides / nitrides), weak interfacial bonding, hydrogen permeation channels caused by microscopic defects (pores, grain boundaries), and high-temperature phase transition failure, making it difficult to meet the requirements of extreme working conditions such as nuclear energy and hydrogen storage and transportation.

[0040] To address the above problems, the present invention provides a method for preparing a high-entropy alloy coating, comprising the following steps: S) depositing a high-entropy alloy coating on the substrate surface using a magnetically filtered cathode vacuum arc deposition method; the target material used in the magnetically filtered cathode vacuum arc deposition includes a nickel-chromium alloy target, a titanium target, an aluminum target, and a vanadium target; the nickel content in the nickel-chromium alloy target is 20~30wt%.

[0041] In this invention, there are no special restrictions on the source of any raw materials; they can be commercially available.

[0042] In this invention, the substrate can be any substrate known to those skilled in the art, and can be selected according to different needs. Specifically, it can be an alloy substrate or a single-crystal silicon substrate; the alloy substrate can be X70 steel or 304 stainless steel.

[0043] In a specific embodiment of the present invention, in order to improve the bonding force between the substrate and the high-entropy alloy coating, it is preferable to pre-treat the substrate first; specifically, the following steps are performed: S1) Pre-treat the substrate; the pre-treat includes grinding and polishing and ion cleaning; S2) Deposit the high-entropy alloy coating on the surface of the pre-treated substrate using a magnetically filtered cathode vacuum arc deposition method.

[0044] In a specific embodiment of the present invention, the grinding and polishing preferably includes coarse grinding, medium grinding, fine grinding and fine polishing performed in sequence; firstly, coarse grinding can remove the oxide layer and welding burrs on the substrate surface, then medium grinding can refine the more obvious scratches on the surface, and finally fine grinding can form a smooth mirror surface.

[0045] In a specific embodiment of the present invention, the coarse grinding is preferably performed using a 200-600 mesh grinding disc, more preferably using a 300-500 mesh grinding disc, and even more preferably using a 400 mesh grinding disc; the type of grinding disc used for coarse grinding can be selected according to the type of substrate, specifically a diamond grinding disc; the coarse grinding time is preferably 0.5-2 hours; optionally, the coarse grinding time is 0.5 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours, or any two of the above values.

[0046] In a specific embodiment of the present invention, the intermediate grinding is preferably performed using an 800-1200 mesh grinding disc, more preferably by first using an 800 mesh grinding disc and then by using a 1200 mesh grinding disc; the type of grinding disc used for intermediate grinding can be selected according to the type of substrate, specifically a diamond grinding disc; the intermediate grinding time is preferably 1-3 hours; optionally, the intermediate grinding time is 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or any two of the above values.

[0047] In a specific embodiment of the present invention, the fine grinding is preferably performed using a 1400-1600 mesh grinding disc, more preferably using a 1500 mesh grinding disc; the type of grinding disc used for fine grinding can be selected according to the type of substrate, specifically a diamond grinding disc; the fine grinding time is preferably 0.5-2 hours; optionally, the fine grinding time is 0.5 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours or any two of the above values.

[0048] In a specific embodiment of the present invention, the fine polishing is preferably performed using polishing powder and polishing cloth with a thickness of 0.5~3 μm, more preferably using polishing powder and polishing cloth with a thickness of 0.5~2 μm, and even more preferably using polishing powder and polishing cloth with a thickness of 1 μm; the polishing powder is preferably alumina polishing powder.

[0049] In a specific embodiment of the present invention, after grinding and polishing, it is preferable to use a solvent for cleaning to remove residual impurities on the surface, specifically by cleaning with alcohol and acetone in sequence; the cleaning method is preferably ultrasonic; the cleaning time with alcohol and acetone is preferably 5 to 30 minutes, more preferably 10 to 20 minutes, and even more preferably 15 minutes.

[0050] In a specific embodiment of the present invention, the substrate after solvent cleaning is subjected to ion cleaning to obtain a pretreated substrate; the ion cleaning is preferably performed using an inert gas; the inert gas can be any inert gas well known to those skilled in the art, and there are no special limitations, specifically it can be argon, and more specifically argon with a purity of 99.99%; the flow rate of the inert gas is preferably 50~200 sccm; optionally, the flow rate of the inert gas is 50 sccm, 80 sccm, 100 sccm, 120 sccm, 150 sccm, 180 sccm, 200 sccm or any two of the above values.

[0051] In one specific embodiment of the present invention, the ion cleaning is preferably performed in a magnetic filter cathode vacuum arc deposition apparatus, and the coating deposition can be performed directly after ion cleaning to avoid introducing other impurities.

[0052] In a specific embodiment of the present invention, in order to reduce the influence of other gases on the deposited coating, it is preferable to perform a vacuum treatment before ion cleaning, and then introduce an inert gas to the working pressure for ion cleaning; the vacuum treatment is preferably below 0.005 Pa.

[0053] In one specific embodiment of the present invention, the working gas pressure of the ion cleaning is preferably 0.01~0.1 Pa; optionally, the working gas pressure of the ion cleaning is 0.01 Pa, 0.02 Pa, 0.03 Pa, 0.04 Pa, 0.05 Pa, 0.06 Pa, 0.07 Pa, 0.08 Pa, 0.09 Pa, 0.1 Pa or any two of the above values.

[0054] In one specific embodiment of the present invention, the current intensity of the ion cleaning is preferably 80~150A; optionally, the current intensity of the ion cleaning is 80 A, 90 A, 100 A, 110 A, 120 A, 130 A, 140 A, 150 A or any two of the above values.

[0055] In one specific embodiment of the present invention, the ion cleaning time is preferably 4 to 12 minutes; optionally, the ion cleaning time is 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes or any two of the above values.

[0056] In a specific embodiment of the present invention, the ion cleaning is preferably performed using a gradient-decreasing negative bias voltage. Using a gradient-decreasing negative bias voltage for ion cleaning can reduce surface damage, improve cleaning uniformity, and optimize surface activity. The number of gradients in the gradient-decreasing negative bias voltage is four, preferably -850V~-750V, -650V~-550V, -450V~-350V, and -250V~-150V; more preferably, the gradient-decreasing negative bias voltage is -820V~-780V, -620V~-580V, -420V~-380V, and -220V~-180V; even more preferably, the gradient-decreasing negative bias voltage is -800V, -600V, -400V, and -200V. The cleaning time for the four gradients can be the same or different, without any particular limitation. In the present invention, the cleaning time for each of the four gradients is preferably 1~3 min, more preferably 2~3 min. min, and preferably 2 min.

[0057] A high-entropy alloy coating is deposited on the surface of a substrate or a pretreated substrate using a magnetically filtered cathode vacuum arc deposition method. In this invention, a magnetically filtered cathode vacuum arc deposition method (FCVA) is used to instantly evaporate the target material and generate a high-density plasma by breaking down the target material surface under vacuum. Through a specially designed magnetic field, the Lorentz force is used to confine charged ions to move along the magnetic field lines, while neutral large particles are blocked because they are uncharged. This achieves the "purification" of the plasma and allows it to be deposited on the substrate surface under the action of a negative bias voltage.

[0058] In one specific embodiment of the present invention, the magnetically filtered cathode vacuum arc deposition employs a multi-arc magnetically filtered cathode deposition system.

[0059] In a specific embodiment of the present invention, the target material used for the magnetically filtered cathode vacuum arc deposition includes a nickel-chromium alloy target, a titanium target, an aluminum target, and a vanadium target; the nickel content in the nickel-chromium alloy target is 20-30 wt%; optionally, the nickel content in the nickel-chromium alloy target is 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, or any two of the above values; the purity of the nickel-chromium alloy target is preferably greater than 99.9%, more preferably 99.95%; the purity of the titanium target is preferably greater than 99%, more preferably greater than 99.5%, and even more preferably 99.8%; the purity of the aluminum target is preferably greater than 99%, more preferably greater than 99.5%, and even more preferably 99.8%; the purity of the vanadium target is preferably greater than 99%, more preferably greater than 99.5%, and even more preferably 99.8%.

[0060] In one specific embodiment of the present invention, during the magnetically filtered cathode vacuum arc deposition, the power of the nickel-chromium alloy target is preferably 2 to 2.5 kW; optionally, the power of the nickel-chromium alloy target is 2 kW, 2.1 kW, 2.2 kW, 2.3 kW, 2.4 kW, 2.5 kW, or any two of the above values.

[0061] In one specific embodiment of the present invention, during the magnetically filtered cathode vacuum arc deposition, the power of the titanium target is preferably 2 to 2.5 kW; optionally, the power of the titanium target is 2 kW, 2.1 kW, 2.2 kW, 2.3 kW, 2.4 kW, 2.5 kW or any two of the above values.

[0062] In one specific embodiment of the present invention, during the magnetically filtered cathode vacuum arc deposition, the power of the aluminum target is preferably 2 to 2.5 kW; optionally, the power of the aluminum target is 2 kW, 2.1 kW, 2.2 kW, 2.3 kW, 2.4 kW, 2.5 kW or any two of the above values.

[0063] In one specific embodiment of the present invention, during the magnetically filtered cathode vacuum arc deposition, the power of the vanadium target is preferably 2 to 2.5 kW; optionally, the power of the vanadium target is 2 kW, 2.1 kW, 2.2 kW, 2.3 kW, 2.4 kW, 2.5 kW or any two of the above values.

[0064] In one specific embodiment of the present invention, the magnetically filtered cathode vacuum arc deposition employs a 90° magnetically filtered bent tube. The present invention utilizes a four-arc magnetically filtered cathode deposition technology system. In a vacuum environment, a high-current arc breaks down the target surface, instantly evaporating the target and generating high-density plasma. The FCVA, through a specially designed magnetic field (such as a 90° bend), uses the Lorentz force to confine charged ions along magnetic field lines, while neutral large particles, being uncharged, are blocked, thereby achieving the "purification" of the plasma and depositing it onto the substrate surface under a negative bias voltage. Figure 1 Schematic diagram of a multi-arc magnetic filter cathode deposition equipment.

[0065] In one specific embodiment of the present invention, an inert gas is introduced to provide working pressure during the magnetically filtered cathode vacuum arc deposition; the inert gas can be any inert gas well known to those skilled in the art, and there are no special restrictions, but argon is preferred in the present invention; the flow rate of the inert gas is preferably 10~50 sccm; optionally, the flow rate of the inert gas is 10 sccm, 20 sccm, 30 sccm, 40 sccm, 50 sccm or any two of the above values.

[0066] In one specific embodiment of the present invention, the working gas pressure of the magnetically filtered cathode vacuum arc deposition is preferably 0.03~2 Pa; optionally, the working gas pressure of the magnetically filtered cathode vacuum arc deposition is 0.03 Pa, 0.045 Pa, 0.05 Pa, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, 1.0 Pa, 1.1 Pa, 1.2 Pa, 1.3 Pa, 1.4 Pa, 1.5 Pa, 1.6 Pa, 1.7 Pa, 1.8 Pa, 1.9 Pa, 2 Pa, or any two of the above values.

[0067] In one specific embodiment of the present invention, the magnetic filtering current intensity of the magnetic filtering cathode vacuum arc deposition is preferably 1~2 A; optionally, the magnetic filtering current intensity of the magnetic filtering cathode vacuum arc deposition is 1 A, 1.1 A, 1.2 A, 1.3 A, 1.4 A, 1.5 A, 1.6 A, 1.7 A, 1.8 A, 1.9 A, 2 A or any two of the above values.

[0068] In one specific embodiment of the present invention, the negative bias voltage of the magnetic filter cathode vacuum arc deposition is preferably less than -80V or greater than or equal to -150V, more preferably less than or equal to -50V or -180V to -220V.

[0069] In one specific embodiment of the present invention, the negative bias voltage of the magnetically filtered cathode vacuum arc deposition is preferably -20V to -50V or -180V to -220V; optionally, the negative bias voltage of the magnetically filtered cathode vacuum arc deposition is -20V, -30V, -40V, -50V or any two of the above values; or optionally, the negative bias voltage of the magnetically filtered cathode vacuum arc deposition is -180V, -190V, -200V, -210V, -220V or any two of the above values.

[0070] In one specific embodiment of the present invention, the negative bias voltage of the magnetic filter cathode vacuum arc deposition is preferably -50V, -150V or -200V.

[0071] In one specific embodiment of the present invention, the duty cycle of the magnetically filtered cathode vacuum arc deposition is preferably greater than or equal to 50%, more preferably 50% to 90%; optionally, the duty cycle of the magnetically filtered cathode vacuum arc deposition is 50%, 60%, 70%, 80%, 90% or any two of the above values.

[0072] In one specific embodiment of the present invention, the time for magnetically filtered cathode vacuum arc deposition is 30 to 240 min; optionally, the time for magnetically filtered cathode vacuum arc deposition is 30 min, 60 min, 90 min, 120 min, 180 min, 240 min or any two of the above times.

[0073] This invention employs a high-entropy alloy coating containing multiple metallic elements to induce a lattice distortion effect, significantly increasing hydrogen diffusion resistance. Its amorphous / nanocrystalline structure eliminates grain boundary defects, blocking hydrogen permeation pathways and improving hydrogen barrier efficiency by 1-2 orders of magnitude compared to traditional coatings. Simultaneously, its high mixing entropy characteristics endow it with excellent high-temperature stability, strong interfacial adhesion, and multifunctional properties such as radiation resistance and corrosion resistance. Furthermore, combined with advanced processes such as multi-arc magnetic filtered cathode deposition (FCVA), ultra-dense, low-defect HEA coatings can be prepared at low temperatures, balancing high hydrogen barrier performance, mechanical strength, and long-term service reliability, providing a breakthrough solution for extreme environments such as nuclear reactor cladding and aerospace hydrogen storage systems.

[0074] The present invention also provides a high-entropy alloy coating prepared by the above preparation method, wherein the high-entropy alloy coating comprises metallic elements nickel, chromium, titanium, aluminum and vanadium; the high-entropy alloy coating is an amorphous high-entropy alloy coating.

[0075] In a specific embodiment of the present invention, the atomic ratio of the metal elements nickel, chromium, titanium, aluminum and vanadium in the high-entropy alloy coating is preferably (0.5~2):(0.5~2):(0.5~2):(0.5~2):(0.5~2), more preferably (0.5~1.5):(0.5~1.5):(0.5~1.5):(0.5~1.5):(0.5~1.5), even more preferably (0.8~1.2):(0.8~1.2):(0.8~1.2):(0.8~1.2):(0.8~1.2), and most preferably (0.9~1.1):(0.9~1.1):(0.9~1.1):(0.9~1.1):(0.9~1.1):(0.9~1.1).

[0076] In one specific embodiment of the present invention, the steady-state hydrogen permeation current of the high-entropy alloy coating is less than 5 µA·cm. -2 .

[0077] In one specific embodiment of the present invention, the steady-state hydrogen permeation current of the high-entropy alloy coating is less than 2 µA·cm. -2 .

[0078] In one specific embodiment of the present invention, the steady-state hydrogen permeation current of the high-entropy alloy coating can reach 0.6 µA·cm. -2 .

[0079] In one specific embodiment of the present invention, the thickness of the high-entropy alloy coating is preferably 0.5~5μm; optionally, the thickness of the high-entropy alloy coating is 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 3 μm, 4 μm, 5 μm or any two of the above values.

[0080] The present invention also provides an apparatus for the field of hydrogen energy, comprising the above-described high-entropy alloy coating.

[0081] In one specific embodiment of the present invention, the device for the hydrogen energy field can be a pipeline, a reactor cladding, a hydrogen storage container, etc.

[0082] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a high-entropy alloy coating and its atomic-level manufacturing method, and its application in the field of hydrogen energy.

[0083] All reagents used in the following examples are commercially available.

[0084] Example 1

[0085] A high-entropy alloy hydrogen-barrier coating is prepared by the following method:

[0086] Step S101: Grinding and polishing:

[0087] The X70 pipeline steel substrate was coarsely ground for 1 hour using a 400-mesh diamond grinding disc to remove the oxide layer and weld burrs.

[0088] The surface was ground for 2 hours at a time using an 800-grit diamond grinding wheel and then a 1200-grit diamond grinding wheel to refine the more obvious scratches.

[0089] Then, use a 1500-grit diamond grinding wheel (smooth mirror surface) for fine grinding for 1 hour; finally, use 1-micron alumina polishing powder + polishing cloth for fine polishing for 0.5 hours.

[0090] After fine polishing, the product is ultrasonically cleaned with alcohol and acetone for 15 minutes each.

[0091] Step S102 Multi-arc magnetic filter cathode deposition:

[0092] Choose as Figure 1The four-arc head magnetically filtered cathode vacuum arc (Co-FVCA) device shown uses NiCr alloy (containing 75 wt.% chromium, 25 wt.% nickel, and 99.95% purity) and three pure metals (titanium, aluminum, and vanadium, with 99.80% purity) as targets. The thickness and diameter of all targets are 20 mm and 100 mm, respectively, and Ar with 99.99% purity is selected as the carrier gas.

[0093] The substrate obtained in step S101 was placed in a vacuum chamber and mounted on a sample stage. After evacuating to below 0.005 Pa, argon gas was introduced at a flow rate of 100 sccm. The working pressure of the vacuum chamber was changed to about 0.04 Pa. The current intensity was 110 A. The substrate surface was sputtered and cleaned for 2 min each time under the condition of successively decreasing negative bias voltage (800V→600V→400V→200V).

[0094] Argon gas with a flow rate of 20 sccm was introduced into the vacuum chamber at a working pressure of 0.045 Pa. The power of each target was 2.3 kW, the magnetic filtering current intensity was 1.8 A, the substrate negative bias voltage was set to -50 V, and the duty cycle was set to 90%. A coating was deposited on the substrate surface for 120 min to obtain a high-entropy alloy hydrogen barrier coating with a thickness of approximately 0.7 μm, marked as 50 V.

[0095] Example 2

[0096] A high-entropy alloy hydrogen-barrier coating is prepared by the following method:

[0097] Step S101: Grinding and polishing:

[0098] The X70 pipeline steel substrate was coarsely ground for 1 hour using a 400-mesh diamond grinding disc to remove the oxide layer and weld burrs.

[0099] The surface was ground for 2 hours at a time using an 800-grit diamond grinding wheel and then a 1200-grit diamond grinding wheel to refine the more obvious scratches.

[0100] Then, use a 1500-grit diamond grinding wheel (smooth mirror surface) for fine grinding for 1 hour; finally, use 1-micron alumina polishing powder + polishing cloth for fine polishing for 0.5 hours.

[0101] After fine polishing, the product is ultrasonically cleaned with alcohol and acetone for 15 minutes each.

[0102] Step S102 Multi-arc magnetic filter cathode deposition:

[0103] A four-arc head magnetically filtered cathode vacuum arc (Co-FVCA) device was selected, using NiCr alloy (containing 75 wt.% chromium, 25 wt.% nickel, and 99.95% purity) and three pure metals (titanium, aluminum, and vanadium, with 99.80% purity) as targets. The thickness and diameter of all targets were 20 mm and 100 mm, respectively, and Ar with 99.99% purity was selected as the carrier gas.

[0104] The substrate obtained in step S101 was placed in the vacuum chamber and mounted on the sample stage. After evacuating to below 0.005 Pa, argon gas was introduced at a flow rate of 100 sccm. The working pressure of the vacuum chamber was changed to about 0.04 Pa. The current intensity was 110 A. The substrate surface was sputtered and cleaned for 2 min each time under the condition of successively decreasing negative bias voltage (800V→600V→400V→200V).

[0105] Argon gas with a flow rate of 20 sccm was introduced into the vacuum chamber at a working pressure of 0.045 Pa. The power of each target was 2.3 kW, the magnetic filtering current intensity was 1.8 A, the substrate negative bias voltage was set to -100 V, and the duty cycle was set to 90%. A coating was deposited on the substrate surface for 120 min to obtain a high-entropy alloy hydrogen barrier coating with a thickness of approximately 1.6 μm, marked as 100 V.

[0106] Example 3

[0107] A high-entropy alloy hydrogen-barrier coating is prepared by the following method:

[0108] Step S101: Grinding and polishing:

[0109] The X70 pipeline steel substrate was coarsely ground for 1 hour using a 400-mesh diamond grinding disc to remove the oxide layer and weld burrs.

[0110] The surface was ground for 2 hours at a time using an 800-grit diamond grinding wheel and then a 1200-grit diamond grinding wheel to refine the more obvious scratches.

[0111] Then, use a 1500-grit diamond grinding wheel (smooth mirror surface) for fine grinding for 1 hour; finally, use 1-micron alumina polishing powder + polishing cloth for fine polishing for 0.5 hours.

[0112] After fine polishing, the product is ultrasonically cleaned with alcohol and acetone for 15 minutes each.

[0113] Step S102 Multi-arc magnetic filter cathode deposition:

[0114] A four-arc head magnetically filtered cathode vacuum arc (Co-FVCA) device was selected, using NiCr alloy (containing 75 wt.% chromium, 25 wt.% nickel, and 99.95% purity) and three pure metals (titanium, aluminum, and vanadium, with 99.80% purity) as targets. The thickness and diameter of all targets were 20 mm and 100 mm, respectively, and Ar with 99.99% purity was selected as the carrier gas.

[0115] The substrate obtained in step S101 was placed in the vacuum chamber and mounted on the sample stage. After evacuating to below 0.005 Pa, argon gas was introduced at a flow rate of 100 sccm. The working pressure of the vacuum chamber was changed to about 0.04 Pa. The current intensity was 110 A. The substrate surface was sputtered and cleaned for 2 min each time under the condition of successively decreasing negative bias voltage (800V→600V→400V→200V).

[0116] Argon gas with a flow rate of 20 sccm was introduced into the vacuum chamber at a working pressure of 0.045 Pa. The power of each target was 2.3 kW, the magnetic filtering current intensity was 1.8 A, the substrate negative bias voltage was set to -150 V, and the duty cycle was set to 90%. A coating was deposited on the substrate surface for 120 min to obtain a high-entropy alloy hydrogen barrier coating with a thickness of approximately 1.3 μm, marked as 150 V.

[0117] Example 4

[0118] A high-entropy alloy hydrogen-barrier coating is prepared by the following method:

[0119] Step S101: Grinding and polishing:

[0120] The X70 pipeline steel substrate was coarsely ground for 1 hour using a 400-mesh diamond grinding disc to remove the oxide layer and weld burrs.

[0121] The surface was ground for 2 hours at a time using an 800-grit diamond grinding wheel and then a 1200-grit diamond grinding wheel to refine the more obvious scratches.

[0122] Then, use a 1500-grit diamond grinding wheel (smooth mirror surface) for fine grinding for 1 hour; finally, use 1-micron alumina polishing powder + polishing cloth for fine polishing for 0.5 hours.

[0123] After fine polishing, the product is ultrasonically cleaned with alcohol and acetone for 15 minutes each.

[0124] Step S102 Multi-arc magnetic filter cathode deposition:

[0125] A four-arc head magnetically filtered cathode vacuum arc (Co-FVCA) device was selected, using NiCr alloy (containing 75 wt.% chromium, 25 wt.% nickel, and 99.95% purity) and three pure metals (titanium, aluminum, and vanadium, with 99.80% purity) as targets. The thickness and diameter of all targets were 20 mm and 100 mm, respectively, and Ar with 99.99% purity was selected as the carrier gas.

[0126] The substrate obtained in step S101 was placed in the vacuum chamber and mounted on the sample stage. After evacuating to below 0.005 Pa, argon gas was introduced at a flow rate of 100 sccm. The working pressure of the vacuum chamber was changed to about 0.04 Pa. The current intensity was 110 A. The substrate surface was sputtered and cleaned for 2 min each time under the condition of successively decreasing negative bias voltage (800V→600V→400V→200V).

[0127] Argon gas with a flow rate of 20 sccm was introduced into the vacuum chamber at a working pressure of 0.045 Pa. The power of each target was 2.3 kW, the magnetic filtering current intensity was 1.8 A, the substrate negative bias voltage was set to -200 V, the duty cycle was set to 90%, and a coating was deposited on the substrate surface. The coating deposition time was 120 min, resulting in a high-entropy alloy hydrogen barrier coating with a thickness of approximately 0.6 μm, marked as 200 V.

[0128] The high-entropy alloy hydrogen barrier coatings obtained in Examples 1-4 were analyzed using X-ray diffraction, and their X-ray images are shown below. Figure 2 As shown. By Figure 2 It can be seen that the structures of the coatings deposited under different negative bias voltages are as follows: the high-entropy alloy coating obtained at -50V has an amorphous crystal structure; the high-entropy alloy coating obtained at -100V has an fcc simple solid solution structure; the high-entropy alloy coating obtained at -150V has an amorphous crystal structure; and the high-entropy alloy coating obtained at -200V has an amorphous crystal structure.

[0129] Figure 3 The images show the HRTEM images and corresponding selected area electron diffraction patterns of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1 and 2.

[0130] The cross-sections of the high-entropy alloy hydrogen barrier coatings obtained in Examples 1-4 were analyzed using scanning electron microscopy, and their scanning electron micrographs are shown below. Figure 4 As shown, (a) is 50V, (b) is 100V, (c) is 150V, and (d) is 200V.

[0131] use Figure 5The apparatus shown was used to perform electrochemical hydrogen permeation tests on X70 pipeline steel and the high-entropy alloy hydrogen-barrier coatings obtained in Examples 1-4, and the hydrogen permeation curves were obtained (based on national standard GB / T 30074-2013, and referenced in the paper "Methodology of the electrochemical hydrogen permeation test: A parametric evaluation" DOI:10.1016 / j.ijhydene.2023.04.211). Figure 6 As shown. By Figure 6 It can be seen that the steady-state hydrogen permeation current of the amorphous high-entropy alloy is 0.6 µA·cm. -2 The steady-state hydrogen permeation current of the high-entropy alloy coating with a crystalline structure deposited at -100V is 13 µA·cm. -2 .

[0132] Figure 7 The figures show the potentiodynamic polarization curves of the high-entropy alloy hydrogen-barrier coatings obtained in Examples 1-4 in a 3.5 wt.% NaCl solution. Corrosion resistance was primarily evaluated using the corrosion current density (icorr), as it is proportional to the corrosion rate. Figure 7 It can be seen that, with the increase of bias voltage, the icorr values ​​of the coating are 0.75, 163.5, 130.9 and 0.3 μA / cm, respectively. 2 .

[0133] In summary, the high-entropy alloy coating provided by this invention can change crystal growth by altering the negative bias voltage of the substrate. The amorphous / nanocrystalline structure can eliminate grain boundary defects, block hydrogen permeation paths, and improve hydrogen blocking efficiency by 1 to 2 orders of magnitude compared to traditional coatings, while improving corrosion resistance by 3 orders of magnitude.

[0134] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method of producing a high-entropy alloy coating, characterized by, The method comprises the following steps: S) depositing a high-entropy alloy coating on the surface of the substrate by a filtered cathodic vacuum arc deposition method; the target material used in the filtered cathodic vacuum arc deposition method comprises a nickel-chromium alloy target, a titanium target, an aluminum target, and a vanadium target; the content of nickel in the nickel-chromium alloy target is 20-30 wt%.

2. The production method according to claim 1, characterized by, The working pressure of the filtered cathodic vacuum arc deposition is 0.03-2 Pa; And / or, the magnetic filtering current intensity of the filtered cathodic vacuum arc deposition is 1-2 A; And / or, the negative bias of the filtered cathodic vacuum arc deposition is less than -80 V or greater than or equal to -150 V; And / or, the duty cycle of the filtered cathodic vacuum arc deposition is greater than or equal to 50%.

3. The preparation method according to claim 2, characterized in that, The negative bias of the filtered cathodic vacuum arc deposition is less than or equal to -50 V or -180 V to -220 V; And / or, the duty cycle of the filtered cathodic vacuum arc deposition is 90%.

4. The method of claim 1, wherein, The power of the nickel-chromium alloy target, the titanium target, the aluminum target, and the vanadium target is independently 2-2.5 kW; And / or, the time of the filtered cathodic vacuum arc deposition is 30-240 min.

5. The preparation method according to claim 1, characterized in that, The step S) is specifically: S1) pretreating the substrate; the pretreatment comprises polishing, ion cleaning, and the like; S2) depositing a high-entropy alloy coating on the surface of the pretreated substrate by a filtered cathodic vacuum arc deposition method.

6. The preparation method according to claim 5, characterized in that, The polishing comprises rough grinding, medium grinding, fine grinding, and fine polishing in sequence; the rough grinding is performed by using a 200-600 mesh grinding disc; the medium grinding is performed by using an 800-1200 mesh grinding disc; the fine grinding is performed by using a 1400-1600 mesh grinding disc; the fine polishing is performed by using a 0.5-3 μm polishing powder and a polishing cloth; And / or, the ion cleaning is performed by using an inert gas; the flow rate of the inert gas is 50-200 sccm; the working pressure of the ion cleaning is 0.01-0.1 Pa; the current intensity of the ion cleaning is 80-150 A; the ion cleaning is performed by using a gradiently reduced negative bias.

7. The preparation method according to claim 6, characterized in that, The gradient number of the gradiently reduced negative bias is 4, and the gradient is -850 V to -750 V, -650 V to -550 V, -450 V to -350 V, and -250 V to -150 V. The time of the ion cleaning is 4-12 min.

8. The high-entropy alloy coating prepared by the method of any one of claims 1-7, characterized in that, The high-entropy alloy coating comprises metal elements nickel, chromium, titanium, aluminum, and vanadium. The high-entropy alloy coating is an amorphous high-entropy alloy coating.

9. The high-entropy alloy coating of claim 8, wherein, The high-entropy alloy coating has a steady-state hydrogen permeation current of less than 5 µA·cm -2 .

10. An apparatus for use in the field of hydrogen energy, characterized in that, The high-entropy alloy coating prepared by the preparation method of any one of claims 1-7 or the high-entropy alloy coating of claim 8 or 9.

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