High-entropy alloy coating for hydrogen resistance and preparation method thereof

Abstract

The invention relates to a high-entropy alloy coating for resisting hydrogen and a preparation method of the high-entropy alloy coating, and belongs to the technical field of hydrogen damage prevention of hydrogen conveying pipelines. The high-entropy alloy coating comprises Al, Fe, Cr, Mo, Ti and Pd, the ratio of the total mass of the Al, the Fe, the Cr, the Mo and the Ti to the mass of the Pd is 1-x: x, and x is larger than or equal to 0 and smaller than or equal to 1. According to the method, the high-entropy alloy target material is obtained by virtue of the advantage of electric arc melting, and the high-entropy alloy coating is obtained on the surface of the pretreated matrix through magnetron sputtering. The corrosion resistance of the high-entropy alloy, the good hydrogen resistance of the alloy formed by elements such as Al, Fe and Cr and the advantages of Pd in the hydrogen storage aspect are perfectly combined, so that the hydrogen resistance of the coating is further improved. The high-entropy alloy coating prepared through the method is controllable in component and performance, the binding force between the coating and a base body is high, and therefore the good hydrogen resistance effect is achieved, the thickness of the coating prepared through the technology is controllable, and the performance of the coating can be conveniently regulated, controlled and tested.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen damage prevention for hydrogen transmission pipelines, and particularly relates to a high-entropy alloy coating for hydrogen blocking and a preparation method thereof. Background Art

[0002] In the hydrogen energy safety storage and rapid transportation and distribution system, due to the small size of hydrogen gas molecules, it is easy to penetrate into the metal interior, causing hydrogen embrittlement, resulting in the failure of equipment or transportation pipelines, leakage, and thus causing significant losses. Therefore, how to effectively reduce hydrogen penetration is one of the urgent problems to be solved in the utilization of hydrogen energy. Covering a coating on the inner surface of hydrogen storage and transportation equipment to prevent the penetration of high-pressure hydrogen is an effective solution. Previously, some researchers proposed using organic coatings or films to effectively reduce the hydrogen permeability. However, the anti-corrosion ability of the coating during actual pipeline transportation must also be ensured, because the harsh humid corrosion environment will also lead to the failure of hydrogen transmission pipelines or equipment, resulting in hydrogen storage and transportation risks. Therefore, it is crucial to develop a coating that can not only effectively reduce hydrogen penetration but also improve the anti-corrosion ability, and it is of great significance for large-scale hydrogen energy utilization.

[0003] High Entropy Alloys (HEAs), which are alloys formed by five or more equal or approximately equal amounts of metals, have been proven to have many excellent properties superior to traditional alloys, such as excellent mechanical properties, high-temperature resistance, wear resistance, and corrosion resistance, and have shown great development potential in many fields. In addition, the common methods for preparing high-entropy alloy coatings currently include arc melting, resistance induction melting, mechanical alloying, laser melting, magnetron sputtering, etc. Among them, arc melting for preparing high-entropy alloys has the advantages of a relatively high melting temperature, small grain size, and uniform composition, but the melting amount per time is less; while magnetron sputtering technology has the advantages of uniform film formation, high film formation rate, low substrate temperature, good coating adhesion, and controllable thickness, and the microstructure of the coating can be adjusted by changing the sputtering process parameters, thereby optimizing the quality and performance of the prepared coating. Summary of the Invention

[0004] In view of the above problems, the present invention provides a high-entropy alloy coating for hydrogen blocking and a preparation method thereof.

[0005] The first object of the present invention is to provide a high-entropy alloy powder coating for hydrogen blocking, the coating comprising Al, Fe, Cr, Mo, Ti, and Pd, and the mass ratio of the total mass of Al, Fe, Cr, Mo, and Ti to the mass of Pd being 1 - x:x, where 0 ≤ x ≤ 1.

[0006] In a specific embodiment of the present invention, the alloy powder coating comprises the following components in mass percentage: Al 5 - 35%, Cr 5 - 35%, Mo 5 - 35%, Ti 5 - 35%, Fe 5 - 35%, and Pd 0.1 - 2%.

[0007] The second object of the present invention is to provide a method for preparing a high-entropy alloy powder coating for hydrogen resistance, to produce the high-entropy alloy powder coating for hydrogen resistance as described above, comprising:

[0008] Melting metal raw materials of Al, Cr, Mo, Ti, Fe, and Pd by arc melting to obtain a target;

[0009] Obtaining a high-entropy alloy powder coating by magnetron sputtering the obtained target on the surface of a pretreated substrate.

[0010] In a specific embodiment of the present invention, the current in the arc melting is 90 - 120 A.

[0011] In a specific embodiment of the present invention, the heating temperature in the arc melting is 800 - 1200 °C.

[0012] In a specific embodiment of the present invention, the number of times of arc melting is 3 - 5 times.

[0013] In a specific embodiment of the present invention, the gas pressure in the magnetron sputtering is 0.5 - 3.0 Pa, and the flow rate of the inert gas is 15 - 40 sccm.

[0014] In a specific embodiment of the present invention, the sputtering power in the magnetron sputtering is 50 - 300 W, and the sputtering time is 5 - 40 min.

[0015] In a specific embodiment of the present invention, the coating thickness is 50 - 200 nm.

[0016] The third object of the present invention is to provide an application of the high-entropy alloy powder coating for hydrogen resistance, and the application of the high-entropy alloy powder coating in a hydrogen transmission pipeline.

[0017] The beneficial effects of the present invention:

[0018] The high-entropy alloy coating for hydrogen resistance provided by the present invention and its preparation method obtain a high-entropy alloy target by virtue of the advantages of arc melting, and a high-entropy alloy coating is obtained on the surface of a pretreated substrate (such as Q235 steel) by magnetron sputtering. In this way, the present invention can complement the advantages of preparing high-entropy alloys by arc melting and preparing metal coatings by magnetron sputtering; the anti-corrosion characteristics of high-entropy alloys, the good hydrogen resistance characteristics of alloys formed by elements such as Al, Fe, and Cr, and the advantages of Pd in hydrogen storage are perfectly combined to further improve the hydrogen resistance performance of the coating. The high-entropy alloy coating prepared by this method is controllable in composition and performance, has a strong bonding force between the coating and the substrate, thereby achieving a good hydrogen resistance effect, and the thickness of the coating prepared by this process is controllable, which is convenient for regulating and testing its performance.

[0019] Other features and advantages of the present invention will be described in the following specification, and, in part, will be obvious from the specification, or will be understood by implementing the present invention. The objectives and other advantages of the present invention can be achieved and obtained by the structures pointed out in the specification, the claims, and the drawings. Brief Description of the Drawings

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0021] Figure 1 The flowchart of a preparation method of a high-entropy alloy powder coating for hydrogen resistance according to an embodiment of the present invention is shown. Detailed Embodiments

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0023] A high-entropy alloy powder coating for hydrogen resistance according to an embodiment of the present invention, the coating includes Al, Fe, Cr, Mo, Ti, and Pd, and the mass ratio of the total mass of Al, Fe, Cr, Mo, and Ti to the mass of Pd is 1 - x:x, where 0 ≤ x ≤ 1.

[0024] In the embodiments of the present invention, the alloy coating comprises the following components in mass percentages: Al 5 - 35%, Cr 5 - 35%, Mo 5 - 35%, Ti 5 - 35%, Fe 5 - 35%, Pd 0.1 - 2%;

[0025] Specifically, the mass percentages of the components of the coating are in accordance with the ratio in Table 1.

[0026] Table 1

[0027] Serial number Al Cr Mo Ti Fe Pd 1 20％ 19％ 19％ 20％ 20％ 2％ 2 20％ 20％ 19％ 19％ 20％ 2％ 3 20％ 19％ 19％ 20％ 20％ 2％ 4 19％ 19％ 18.8％ 20％ 22％ 1.2％ 5 25％ 18％ 18.5％ 20％ 17％ 1.5％ 6 20％ 19％ 18.5％ 19％ 21％ 1.5％ 7 19％ 20％ 18％ 20％ 21％ 2％ 8 22％ 19％ 19％ 18％ 20％ 2％

[0028] As Figure 1 shown, in some embodiments of the present invention, a method for preparing a high-entropy alloy powder coating for hydrogen resistance is provided, and the high-entropy alloy powder coating for hydrogen resistance as described above is prepared, including:

[0029] Arc melting the metal raw materials of Al, Cr, Mo, Ti, Fe, and Pd to obtain a target;

[0030] The obtained target is magnetron sputtered on the surface of the pretreated substrate to obtain a high-entropy alloy powder coating;

[0031] Wherein, the substrate is the steel of a pipeline for hydrogen energy transportation, such as Q235 steel, and the pretreatment includes grinding, polishing, cleaning, and drying to remove the oil stain on the surface of the substrate and improve the adhesion between the substrate and the high-entropy alloy powder coating;

[0032] The operations of grinding, polishing, cleaning, and drying the substrate are common knowledge well-known to those skilled in the art, and thus, they will not be elaborated in the present invention.

[0033] In the embodiments of the present invention, the current in the arc melting is 90 - 120 A, and the specific values of the current are 90 A, 95 A, 100 A, 105 A, 110 A, 115 A, 120 A

[0034] In the embodiments of the present invention, the heating temperature in the arc melting is 800 - 1200 °C, and the heating temperature is any one of 800 °C, 810 °C, 820 °C, 830 °C, 840 °C, 850 °C, 860 °C, 870 °C, 880 °C, 890 °C, 900 °C, 910 °C, 920 °C, 930 °C, 940 °C, 950 °C, 960 °C, 970 °C, 980 °C, 990 °C, 1000 °C, 1010 °C, 1020 °C, 1030 °C, 1040 °C, 1050 °C, 1060 °C, 1070 °C, 1080 °C, 1090 °C, 1100 °C, 1110 °C, 1120 °C, 1130 °C, 1140 °C, 1150 °C, 1160 °C, 1170 °C, 1180 °C, 1190 °C, 1200 °C.

[0035] In the embodiments of the present invention, the number of times of arc melting is 3 - 5 times.

[0036] In the embodiments of the present invention, in the magnetron sputtering, the gas pressure is 0.5 - 3.0 Pa, the flow rate of the inert gas is 15 - 40 sccm. The specific flow rate of the inert gas is any one of 15 sccm, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm; the specific value of the gas pressure is any one of 0.5 Pa, 1 Pa, 1.5 Pa, 2.0 Pa, 2.5 Pa, 3.0 Pa. The inert gas is nitrogen or argon, preferably argon.

[0037] In the embodiments of the present invention, in the magnetron sputtering, the sputtering power is 50 - 300 W. The specific value of the sputtering power is any one of 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, 110 W, 120 W, 130 W, 140 W, 150 W, 160 W, 170 W, 180 W, 190 W, 200 W, 210 W, 220 W, 230 W, 240 W, 250 W, 260 W, 270 W, 280 W, 290 W, 300 W;

[0038] the sputtering time is 5 - 40 min. The specific value of the sputtering time is any one of 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min;

[0039] the thickness of the coating obtained by magnetron sputtering is 50 - 200 nm. The specific value of the coating thickness is any one of 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm.

[0040] Example 1

[0041] Preparation of the high - entropy alloy powder coating:

[0042] Step 1: Place the Al wire, Cr wire, Mo wire, Ti wire, Fe wire and Pd wire in acetone solution respectively, ultrasonically clean to remove the surface oil stain, then ultrasonically clean with ethanol and dry for standby;

[0043] Among them, the ultrasonic cleaning time is 5 min for all;

[0044] Step 2: Place the cleaned Al wire, Cr wire, Mo wire, Ti wire, Fe wire and Pd wire in a crucible according to the mass ratio of No. 1 - 8 in Table 1, and repeatedly arc - melt under the protection of an argon atmosphere to form a high - entropy alloy ingot;

[0045] Among them, the process parameters of arc melting are as follows: the current is 100 A, the heating temperature is 1000 °C, and it is melted repeatedly 4 times.

[0046] Step 3: Cut the high-entropy alloy ingot obtained in Step 2 into circular wafers of a certain size. After ultrasonic cleaning in acetone and ethanol solutions for 5 minutes respectively, let it dry naturally for standby to obtain high-entropy alloy target wafers for magnetron sputtering.

[0047] Among them, the size of the circular wafer is 25.4 * 0.1 mm.

[0048] Step 4: Grind and polish the Q235 steel substrate with a thickness of 0.5 mm with sandpaper, then put it into ethanol and acetone respectively for ultrasonic cleaning for 10 minutes, then clean it with deionized water, and dry it for use.

[0049] Step 5: Use the high-entropy alloy target wafer to perform magnetron sputtering on the Q235 steel substrate obtained in Step 4 when the vacuum degree reaches 1×10 -4 ;

[0050] Among them, the magnetron sputtering gas pressure is 1 Pa, the argon gas flow rate is 15 sccm, the sputtering power is 200 W, the sputtering time is 3 minutes, and the coating thickness is 100 nm.

[0051] Perform corrosion resistance test and hydrogen barrier performance test on the obtained coating, and the obtained results are shown in Table 2.

[0052] Table 2

[0053] Serial number Salt spray test for 100 h Hydrogen permeation reduction factor (PRF) 1 No obvious corrosion 683.2 2 No obvious corrosion 523.1 3 No obvious corrosion 429.3 4 No obvious corrosion 768.4 5 No obvious corrosion 861.5 6 No obvious corrosion 589.8 7 No obvious corrosion 733.9 8 No obvious corrosion 691.4

[0054] From the data in Table 1, it can be seen that the alloy coating obtained by the present invention has good corrosion resistance and hydrogen barrier effect.

[0055] Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-entropy alloy powder coating for hydrogen barrier, Characterized in that, The coating includes Al, Fe, Cr, Mo, Ti and Pd, and the mass ratio of the total mass of Al, Fe, Cr, Mo and Ti to the mass of Pd is 1 - x:x, where 0 ≤ x ≤ 1.

2. The high-entropy alloy powder coating for hydrogen barrier according to claim 1, Characterized in that, It includes the following components in mass percentage: Al 5 - 35%, Cr 5 - 35%, Mo 5 - 35%, Ti 5 - 35%, Fe 5 - 35%, Pd 0.1 - 2%.

3. A preparation method of a high-entropy alloy powder coating for hydrogen barrier, Characterized in that, To make the high-entropy alloy powder coating for hydrogen barrier described in claim 1 or 2, it includes: Arc melting the metal raw materials of Al, Cr, Mo, Ti, Fe and Pd to obtain a target; The obtained target is magnetron sputtered on the surface of the pretreated substrate to obtain a high-entropy alloy powder coating.

4. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to claim 3, Characterized in that, The current in the arc melting is 90 - 120A.

5. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to claim 3, Characterized in that, The heating temperature in the arc melting is 800 - 1200°C.

6. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to claim 3, Characterized in that, The number of times of arc melting is 3 - 5 times.

7. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to claim 3, Characterized in that, The gas pressure in the magnetron sputtering is 0.5 - 3.0 Pa, and the flow rate of the inert gas is 15 - 40 sccm.

8. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to claim 3, Characterized in that, The sputtering power in the magnetron sputtering is 50 - 300 W, and the sputtering time is 5 - 40 min.

9. The preparation method of a high-entropy alloy powder coating for hydrogen barrier according to any one of claims 4 - 8, Characterized in that, The thickness of the coating is 50 - 200 nm.

10. An application of a high-entropy alloy powder coating for hydrogen barrier, Characterized in that, The application of the high-entropy alloy powder coating described in claim 1 or 2 in a hydrogen transmission pipeline.

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