A hydrogen-blocking high-entropy alloy coating and a method for preparing the same

Abstract

The present application relates to a kind of high-entropy alloy coating for hydrogen blocking and preparation method thereof, belong to and hydrogen pipeline hydrogen damage prevention technical field.The high-entropy alloy 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, wherein, 0≤x≤1.The high-entropy alloy target material is obtained by virtue of electric arc smelting advantage, and the high-entropy alloy coating is obtained on the surface of pretreated substrate by magnetron sputtering.The corrosion resistance of high-entropy alloy, the good hydrogen blocking characteristics of alloy formed by Al, Fe, Cr and other elements, and the advantages of Pd in hydrogen storage are perfectly combined to further improve the hydrogen blocking performance of the coating.The high-entropy alloy coating prepared by the method is controllable in composition and performance, and the coating has strong adhesion to the substrate, thereby achieving good hydrogen blocking effect, and the coating prepared by the process is controllable in thickness, which is convenient for performance regulation and testing.

Description

Technical Field

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

[0002] In the safe storage and rapid distribution system of hydrogen energy, hydrogen gas molecules are small and can easily penetrate into the metal, causing hydrogen embrittlement, leading to failure of equipment or transportation pipelines, leakage and significant losses. Therefore, how to effectively reduce hydrogen permeation is one of the urgent problems to be solved in the use of hydrogen energy. Preventing the penetration of high-pressure hydrogen by covering the inner surface of hydrogen storage and transportation equipment with a coating is an effective solution. Previously, researchers have proposed the use of organic coatings or membranes to effectively reduce the permeability of hydrogen. However, the corrosion resistance of the coating must also be guaranteed during actual pipeline transportation. This is because harsh humid and corrosive environments can also cause failure of hydrogen pipelines or equipment, leading to risks in hydrogen storage and transportation. Therefore, it is crucial to develop a coating that can effectively reduce hydrogen permeation and improve corrosion resistance, and it is of great significance for large-scale hydrogen energy utilization.

[0003] High entropy alloys (HEAs) are alloys composed of five or more metals in equal or approximately equal amounts. They have been shown to possess numerous superior properties over traditional alloys, such as excellent mechanical properties, high-temperature resistance, wear resistance, and corrosion resistance, and have shown great development potential in many fields. Currently, common methods for preparing HEAs coatings include arc melting, resistance induction melting, mechanical alloying, laser melting, and magnetron sputtering. Among them, the advantages of arc melting for preparing HEAs are high melting temperatures, small grain sizes, and uniform composition, but the amount of material melted each time is relatively small. Magnetron sputtering technology, on the other hand, offers advantages such as uniform film formation, high film formation rate, low substrate temperature, good coating adhesion, and controllable thickness. Furthermore, by varying the sputtering process parameters, the micromorphology of the coating can be controlled, thereby optimizing the quality and performance of the resulting coating. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a high entropy alloy coating for hydrogen barrier and a preparation method thereof.

[0005] The first object of the present invention is to provide a high entropy alloy powder coating for hydrogen barrier, wherein the coating comprises Al, Fe, Cr, Mo, Ti and Pd, and the mass ratio of the total mass of Al, Fe, Cr, Mo and Ti to Pd is 1-x:x, wherein 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] A second object of the present invention is to provide a method for preparing a high entropy alloy powder coating for hydrogen barrier, wherein the method comprises:

[0008] The target material is obtained by arc melting Al, Cr, Mo, Ti, Fe and Pd metal raw materials;

[0009] The obtained target material is magnetron sputtered on the surface of a pretreated substrate to obtain a high entropy alloy powder coating.

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

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

[0012] In a specific embodiment of the present invention, the arc melting is performed 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 inert gas flow rate is 15-40 sccm.

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

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

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

[0017] Beneficial effects of the present invention:

[0018] The high entropy alloy coating for hydrogen resistance and its preparation method provided by the present invention obtain a high entropy alloy target by virtue of the advantages of arc melting, and obtain a high entropy alloy coating by magnetron sputtering on the surface of a pretreated substrate (such as Q235 steel). In the above manner, the present invention can complement the advantages of arc melting to prepare high entropy alloys and magnetron sputtering to prepare metal coatings; the corrosion resistance of high entropy alloys, the good hydrogen resistance properties of Al, Fe, Cr and other elements after forming alloys, and the advantages of Pd in ​​storing hydrogen 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, and the coating has a strong bonding force with 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 description, and in part will become apparent from the description, or will be understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0021] Figure 1 A flow chart of a method for preparing a high entropy alloy powder coating for hydrogen barrier according to an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

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

[0024] In an embodiment of the present invention, the alloy 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%;

[0025] Specifically, the mass percentages of the components of the coating are in accordance with the ratios 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] like Figure 1 As shown, in certain embodiments of the present invention, a method for preparing a high entropy alloy powder coating for hydrogen barrier is provided, wherein the method comprises:

[0029] The target material is obtained by arc melting Al, Cr, Mo, Ti, Fe and Pd metal raw materials;

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

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

[0032] The grinding, polishing, cleaning and drying operations of the substrate are common knowledge known to those skilled in the art and will not be described in detail herein.

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

[0034] In the embodiment of the present invention, the heating temperature in the arc melting is 800-1200°C, and the heating temperature is 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, 99 Any one of 0℃, 1000℃, 1010℃, 1020℃, 1030℃, 1040℃, 1050℃, 1060℃, 1070℃, 1080℃, 1090℃, 1100℃, 1110℃, 1120℃, 1130℃, 1140℃, 1150℃, 1160℃, 1170℃, 1180℃, 1190℃, and 1200℃.

[0035] In an embodiment of the present invention, the arc melting is performed 3-5 times.

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

[0037] In an embodiment of the present invention, the sputtering power in the magnetron sputtering is 50 to 300 W, and 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, and 300 W.

[0038] The sputtering time is 5-40 min, and 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, and 40 min;

[0039] The coating thickness obtained in the magnetron sputtering is 50 to 200 nm, and 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, and 200 nm.

[0040] Example 1

[0041] Preparation of high entropy alloy powder coating:

[0042] Step 1: placing Al wire, Cr wire, Mo wire, Ti wire, Fe wire and Pd wire in acetone solution, ultrasonically cleaning to remove surface oil, then ultrasonically cleaning with ethanol, drying and setting aside;

[0043] Among them, the ultrasonic cleaning time was 5 min;

[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 sequence numbers 1 to 8 in Table 1, and repeatedly arc melt under argon atmosphere to form a high-entropy alloy ingot;

[0045] The process parameters of arc melting are: current of 100A, heating temperature of 1000°C, and repeated melting 4 times.

[0046] Step 3: Cut the high entropy alloy ingot obtained in step 2 into discs of a certain size, ultrasonically clean them in acetone and ethanol solutions for 5 minutes respectively, and then dry them naturally for use to obtain high entropy alloy target sheets for magnetron sputtering.

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

[0048] Step 4: After grinding and polishing a Q235 steel substrate with a thickness of 0.5 mm with sandpaper, the substrate was ultrasonically cleaned in ethanol and acetone for 10 minutes respectively, and then cleaned with deionized water and dried for later use.

[0049] Step 5: Use high entropy alloy target sheet to reach a vacuum degree of 1×10 -4 The Q235 steel substrate obtained in step 4 is subjected to magnetron sputtering;

[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 min, and the coating thickness is 100 nm.

[0051] The coating obtained above was subjected to corrosion resistance test and hydrogen barrier performance test, and the results are shown in Table 2.

[0052] Table 2

[0053] Serial number Salt spray resistance test 100h 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein; and these modifications or replacements do not cause the essence of the corresponding technical solutions to 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 comprises Al, Fe, Cr, Mo, Ti and Pd, and the mass ratio of the total mass of Al, Fe, Cr, Mo and Ti to Pd is 100-x:x, wherein 0.1≤x≤2; It includes the following components in mass percentage: Al 5-35%, Cr 5-35%, Mo 5-35%, Ti 5-35%, Fe 5-35%, and Pd0.1-2%.

2. A method for preparing a high entropy alloy powder coating for hydrogen barrier, characterized in that: The high entropy alloy powder coating for hydrogen barrier according to claim 1 is prepared, comprising: The target material is obtained by arc melting Al, Cr, Mo, Ti, Fe and Pd metal raw materials; The obtained target material is magnetron sputtered on the surface of the pretreated substrate to obtain a high entropy alloy powder coating; The inert gas flow rate in the magnetron sputtering is 15-40 sccm, and the sputtering time is 5-40 min.

3. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to claim 2, characterized in that: The current during the arc melting is 90-120 A.

4. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to claim 2, characterized in that: The heating temperature in the arc melting is 800-1200°C.

5. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to claim 2, characterized in that: The arc melting is performed 3-5 times.

6. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to claim 2, characterized in that: The gas pressure in the magnetron sputtering is 0.5 ~ 3.0 Pa.

7. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to claim 2, characterized in that: The sputtering power in the magnetron sputtering is 50 to 300 W.

8. The method for preparing a high entropy alloy powder coating for hydrogen barrier according to any one of claims 3 to 7, characterized in that: The coating thickness is 50 to 200 nm.

9. An application of a high entropy alloy powder coating for hydrogen barrier, characterized in that: Use of the high entropy alloy powder coating according to claim 1 in a hydrogen transmission pipeline.

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