High-entropy alloy flux-cored wire, preparation method and method for preparing hydrogen embrittlement-resistant high-entropy alloy coating

Abstract

The high-entropy alloy flux-cored wire comprises a flux core and a welding skin, the flux core is composed of, by mass, 5%-10% of Co, 10%-20% of Cr, 10%-15% of Ni, 20%-30% of Al, 15%-35% of Mn and 1%-5% of La2O3, and the sum of the mass percentages of the components is 100%. The invention further discloses a preparation method of the high-entropy alloy flux-cored wire, the flux-cored powder is wrapped in the FeCoNi strip, the FeCoNi strip is closed, a welding wire precursor is subjected to multi-pass cold-drawing and diameter-reducing wire-drawing die, and finally the high-entropy alloy flux-cored wire is obtained through straightening, disc forming and sealed packaging. When the high-entropy alloy flux-cored wire is used for a hydrogen embrittlement-resistant coating on the inner surface of a stainless steel hydrogen storage tank, the hydrogen permeation resistance and hydrogen embrittlement resistance effects are remarkably improved compared with a stainless steel substrate, and the problem that the stainless steel hydrogen storage tank is prone to hydrogen embrittlement under long-term high-pressure, low-temperature and hydrogen environment exposure can be effectively solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal material surface engineering, specifically relates to a high-entropy alloy flux-cored wire, also relates to a preparation method of the high-entropy alloy flux-cored wire, and also relates to a method for preparing a hydrogen embrittlement-resistant high-entropy alloy coating by using the high-entropy alloy flux-cored wire. Background Art

[0002] As a key device in the application of hydrogen energy, the main function of a hydrogen storage tank is to safely and efficiently store hydrogen under high pressure, low pressure or extremely low temperature conditions. Its design and manufacture need to consider the high-pressure storage of hydrogen, low-temperature characteristics and corrosion resistance of materials to ensure its safety and reliability in various application scenarios. As a traditional metal material, stainless steel has the characteristics of high strength, excellent corrosion resistance, good weldability, good temperature adaptability, low cost, etc. These advantages make stainless steel an important choice for the manufacturing material of hydrogen storage tanks. However, when stainless steel stores high-pressure hydrogen for a long time, hydrogen may penetrate into the steel, causing the material to become brittle. This phenomenon is called hydrogen embrittlement, which may affect the safety and service life of the hydrogen storage tank.

[0003] In order to overcome this limitation of easy hydrogen embrittlement and improve the hydrogen permeation resistance, hydrogen storage performance, corrosion resistance and overall performance of stainless steel tanks, preparing a modified coating on the inner surface of the stainless steel hydrogen storage tank is an effective method to improve the comprehensive performance of the tank. The clad layer material of the hydrogen storage tank needs to have characteristics such as high hydrogen permeation resistance, good bonding strength, corrosion resistance, mechanical properties and thermal stability to cope with the complex tests under long-term high pressure, low temperature and hydrogen environment exposure. The four unique effects of high-entropy alloys, namely the high-entropy effect, "cocktail" effect, lattice distortion effect and sluggish diffusion effect, make high-entropy alloys have excellent high-temperature resistance, corrosion resistance, oxidation resistance, biocompatibility, as well as good electromagnetic and thermodynamic stability; and due to their unique structural and functional characteristics, high-entropy alloys have attracted extensive attention in the field of hydrogen storage. The change in the atomic radius of the metal components in the high-entropy alloy will cause significant lattice distortion and generate a large amount of void space. Hydrogen atoms tend to occupy these voids, thereby increasing the binding energy of hydrogen in the matrix. The diverse composition of elements in the high-entropy alloy helps to design special hydrogen storage materials, demonstrating their great potential in promoting hydrogen storage technology. Therefore, using high-entropy alloy materials as the clad layer of the stainless steel hydrogen storage tank can effectively improve the comprehensive hydrogen storage performance including the hydrogen permeation resistance, corrosion resistance and mechanical properties of the tank. TIG cladding technology is a precise metal surface modification method with advantages such as high energy density, precise control, low heat input and high-quality coating, and is particularly suitable for occasions with strict requirements for the heat influence of the substrate, such as the surface coating of hydrogen storage tanks, and can achieve high-performance and low-defect coating deposition, improving the hydrogen embrittlement resistance and corrosion resistance of materials. Summary of the Invention

[0004] The first object of the present invention is to provide a high-entropy alloy flux-cored wire, which has excellent hydrogen permeation resistance and hydrogen embrittlement resistance when used as an anti-hydrogen embrittlement coating inside a stainless steel hydrogen storage tank.

[0005] The second object of the present invention is to provide a preparation method of the high-entropy alloy flux-cored wire.

[0006] The third object of the present invention is to provide a method for preparing an anti-hydrogen embrittlement high-entropy alloy coating using the high-entropy alloy flux-cored wire.

[0007] The first technical solution adopted by the present invention is a high-entropy alloy flux-cored wire, which includes a flux core and a welding skin. The flux core is composed of the following components by mass percentage: Co: 5% - 10%, Cr: 10% - 20%, Ni: 10% - 15%, Al: 20% - 30%, Mn: 15% - 35%, La2O3: 1% - 5%, and the sum of the mass percentages of the above components is 100%.

[0008] The second technical solution adopted by the present invention is a preparation method of the high-entropy alloy flux-cored wire, which is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution. Step 2: Weigh the following components by mass percentage: Co: 5% - 10%, Cr: 10% - 20%, Ni: 10% - 15%, Al: 20% - 30%, Mn: 15% - 35%, La2O3: 1% - 5%, and the sum of the mass percentages of the above components is 100%. Step 3: Put the powder in Step 2 into a mixer for dry mixing and drying to obtain the flux core powder. Step 4: Wrap the flux core powder obtained in Step 3 inside the FeCoNi strip through a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor. Step 5: Perform multi-pass cold drawing and reducing through a wire drawing die on the wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm. Wipe the oil stain on the wire with a cotton cloth, and finally straighten the wire, coil it into a disk, and seal and package it through a wire drawing machine to obtain the high-entropy alloy flux-cored wire.

[0009] The present invention is also characterized in that In Step 1, the mass fraction of the ethanol solution is 90 - 95%, the ultrasonic cleaning time is 5 - 8 min, and the frequency is 35 - 40 kHz.

[0010] In Step 5, the specific process of the multi-pass cold drawing and reducing wire drawing die is: sequentially pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

[0011] The third technical solution adopted in the present invention is a method for preparing a high-entropy alloy coating resistant to hydrogen embrittlement using a high-entropy alloy flux-cored wire, specifically: The high-entropy alloy flux-cored wire is cladded on the inner surface of the hydrogen storage tank body, and the cladding method is TIG welding cladding. Among them, the welding current is 120A - 140A, the cladding speed is 0.10m / min - 0.20m / min. During cladding, argon is introduced for protection, the welding method is double-layer multi-pass welding, and the bead overlap rate during the cladding process is 30% - 40%.

[0012] The beneficial effects of the present invention are as follows: (1) The high-entropy alloy flux-cored wire of the present invention, when used for the hydrogen embrittlement-resistant coating on the inner surface of the stainless steel hydrogen storage tank, has significantly improved hydrogen permeation resistance and hydrogen embrittlement resistance compared to the stainless steel substrate, and can effectively solve the problem of easy hydrogen embrittlement of the stainless steel hydrogen storage tank body under long-term high pressure, low temperature, and hydrogen environment exposure; (2) The high-entropy alloy flux-cored wire of the present invention has good weldability, good weld bead formation under the TIG welding process, and no welding defects such as porosity, inclusion, oxidation, and crack, and the prepared coating has good bonding with the substrate.

[0013] (3) The high-entropy alloy flux-cored wire of the present invention has high economy, simple equipment process requirements, convenient operation, and is suitable for mass production and the repair of hydrogen storage tank bodies. Description of the Drawings

[0014] Figure 1 is the metallographic microstructure diagram of the high-entropy alloy flux-cored wire coating prepared under the TIG welding conditions of Example 4 in the present invention at 200μm; Figure 2 is the metallographic microstructure diagram of the high-entropy alloy flux-cored wire coating prepared under the TIG welding conditions of Example 4 in the present invention at 100μm; Figure 3 is the metallographic microstructure diagram of the high-entropy alloy flux-cored wire coating prepared under the TIG welding conditions of Example 4 in the present invention at 50μm. Detailed Embodiments

[0015] The present invention will be described in detail below with reference to the drawings and specific embodiments.

[0016] The high-entropy alloy flux-cored wire of the present invention includes two parts: a flux core and a welding skin, and the filling rate of the flux core is 30wt% - 40wt%; The flux core is composed of the following components by mass percentage: Co: 5% - 10%, Cr: 10% - 20%, Ni: 10% - 15%, Al: 20% - 30%, Mn: 15% - 35%, La2O3: 1% - 5%, and the sum of the mass percentages of the above components is 100%; The welding skin is a FeCoNi strip, and the welding skin is composed of the following components by mass percentage: Cr: 0.005%, Cu: 0.015%, Si: 0.2%, Mn: 0.26%, Co: 17.50%, Ni: 30.0%, and Fe is the balance. The sum of the mass percentages of the above components is 100%; The functions of each elemental component in the flux cored wire are as follows: Co, Ni: These two elements and the Fe element belong to the same period and the same group in the periodic table of elements. Therefore, they have similar atomic numbers and atomic radii, and are prone to form substitutional solid solutions. Substitutional solid solutions can form infinite solid solutions. Therefore, they are often used as main element elements in the design of high-entropy alloys. The addition of Co improves the hardness and corrosion resistance of the alloy, and the affinity of Co with H is relatively low, which helps to reduce the dissolution and diffusion of hydrogen in the alloy; Ni can enhance the ductility and corrosion resistance of the alloy, and the Ni element can form a dense oxide film, effectively blocking the passage of hydrogen.

[0017] Cr: It can significantly improve the oxidation resistance and corrosion resistance of the alloy, can also improve the interface bonding strength and adaptability, improve the brittleness of the alloy, and also promote the formation of the BCC phase to improve the wear resistance of the high-entropy alloy coating. And Cr can form a stable chromium oxide layer, and this oxide layer has a low hydrogen permeability.

[0018] Al: It has multiple functions such as reducing density, enhancing oxidation resistance and corrosion resistance, increasing strength and hardness, improving ductility and toughness, regulating phase structure and grain size, and improving heat resistance. And Al can form a dense aluminum oxide layer, playing the role of a hydrogen diffusion barrier.

[0019] Mn: Appropriate addition of the Mn element has a positive effect on improving the weld bead morphology, can effectively reduce the deformation degree during the welding process, and reduce the formation of cracks. And Mn can also form a stable hydride with hydrogen, thereby capturing hydrogen atoms and reducing their diffusion.

[0020] La2O3: By improving the hydrogen absorption capacity, improving the hydrogen diffusion performance, enhancing the surface catalytic activity, stabilizing the formation and decomposition of hydrides, and improving the mechanical properties of the material, the hydrogen storage performance of the high-entropy alloy is significantly improved.

[0021] The preparation method of the high-entropy alloy flux cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90-95%, the ultrasonic cleaning time is 5-8 min, and the frequency is 35-40 kHz.

[0022] Step 2: Weigh the following components by mass percentage: Co: 5% - 10%, Cr: 10% - 20%, Ni: 10% - 15%, Al: 20% - 30%, Mn: 15% - 35%, La2O3: 1% - 5%. The sum of the mass percentages of the above components is 100%; The particle size of the above metal powder is not greater than 150 μm.

[0023] Step 3: Put the powder in Step 2 into a mixer for dry mixing. After the powder is fully mixed, dry it. The drying temperature is 150 - 200 °C and the drying time is 25 - 30 min to obtain the flux-cored powder; Step 4: Wrap the flux-cored powder obtained in Step 3 with an FeCoNi strip by a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm; Step 5: Perform multi-pass cold drawing and reducing through a wire drawing die on the wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm. Finally, wipe the oil stains on the wire with a cotton cloth dipped in anhydrous ethanol or acetone. Finally, straighten the wire through a wire drawing machine, coil it into a disk, and seal and package it to obtain the high-entropy alloy flux-cored wire The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: successively pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

[0024] The method for preparing a hydrogen embrittlement-resistant high-entropy alloy coating using the high-entropy alloy flux-cored wire of the present invention is as follows: Clad the high-entropy alloy flux-cored wire on the inner surface of the hydrogen storage tank body. The cladding method is TIG welding cladding. Among them, the welding current is 120 A - 140 A, the cladding speed is 0.10 m / min - 0.20 m / min. Argon is introduced for protection during cladding. The welding method is double-layer multi-pass welding, and the bead overlap rate during the cladding process is 30% - 40%.

[0025] Example 1 The preparation method of the high-entropy alloy flux-cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90%, ultrasonic cleaning for 5 min, and the frequency is 35 kHz.

[0026] Step 2: For the flux-cored wire, weigh the following components by mass percentage: Co: 10%, Cr: 20%, Ni: 15%, Al: 30%, Mn: 24%, La2O3: 1%. The sum of the mass percentages of the above components is 100%; Step 3: Put the mixed powder prepared in Step 2 into a mixer for dry mixing. After the powder is fully mixed, put the powder into a drying oven for drying at a temperature of 150°C for 30 minutes. After drying, the flux-cored powder is obtained. Step 4: Wrap the flux-cored powder obtained in Step 3 around the FeCoNi strip by a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm. Step 5: Subject the wire precursor obtained in Step 4 to multi-pass cold drawing and reducing through a wire drawing die to obtain a wire with a diameter of 1.42 mm; wipe the oil stain on the wire with a cotton cloth dipped in anhydrous ethanol or acetone, and finally straighten the wire through a wire drawing machine, coil it into a disk, and seal and package it.

[0027] The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: successively pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

[0028] The welding process of the high-entropy alloy flux-cored wire prepared in Example 1 is as follows: tungsten inert gas welding (TIG) is adopted, the welding current is 130 A, the voltage is 15 - 20 V, the welding speed is 0.15 m / min, and pure argon is selected as the shielding gas. When using this wire for welding, the arc is stable, the weld formation is beautiful, and there are no defects such as pores, inclusions, cracks, and oxidation. The microhardness of the obtained high-entropy alloy coating reaches 500 HV. 0.5 , the corrosion current density of the cladding layer is 1.5×10 -4 A·cm -2 , the hydrogen diffusion coefficient is 2.35×10 -6 cm 2 / s, which is lower than that of the base material of the hydrogen storage tank body, and the hydrogen diffusion coefficient is smaller (the corrosion current density of the base material is 1.6×10 -4 A·cm -2 and the hydrogen diffusion coefficient is 2.98×10 -6 cm 2 / s), and the corrosion resistance and hydrogen resistance of the cladding layer are improved.

[0029] Example 2 The preparation method of the high-entropy alloy flux-cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90%, ultrasonically clean for 5 minutes, and the frequency is 35 kHz.

[0030] Step 2: Prepare the flux-cored wire. Weigh the following components by mass percentage to form: Co: 10%, Cr: 20%, Ni: 15%, Al: 24%, Mn: 30%, La2O3: 1%. The sum of the mass percentages of the above components is 100%; Step 3: Put the mixed powder obtained in Step 2 into a mixer for dry mixing. After the powder is fully mixed, put the powder into a drying oven for drying. The temperature is 150 °C and the drying time is 30 min. After drying, the flux-cored powder is obtained; Step 4: Wrap the flux-cored powder obtained in Step 3 around the FeCoNi strip by a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm; Step 5: Perform multi-pass cold drawing and reducing through a wire drawing die on the wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm; Wipe the oil stains on the wire with a cotton cloth dipped in anhydrous ethanol or acetone, and finally straighten the wire through a wire drawing machine, coil it into a disc, and seal and package it.

[0031] The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: Pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm in sequence.

[0032] The welding process of the high-entropy alloy flux-cored wire prepared in Example 2 is as follows: Use tungsten inert gas welding (TIG). The welding current is 130 A, the voltage is 15 - 20 V, the welding speed is 0.15 m / min, and the shielding gas is pure argon. When using this wire for welding, the arc is stable, the weld formation is beautiful, and there are no defects such as pores, inclusions, cracks, and oxidation. The microhardness of the obtained high-entropy alloy coating reaches 536 HV 0.5 , the corrosion current density of the cladding layer is 1.32×10 -4 A·cm -2 , the hydrogen diffusion coefficient is 2.10×10 -6 cm 2 / s. Compared with the corrosion current density of the hydrogen storage tank body base material, it is lower, and the hydrogen diffusion coefficient is smaller (the corrosion current density of the base material is 1.6×10 -4 A·cm -2 and the hydrogen diffusion coefficient is 2.98×10 -6 cm 2 / s). The corrosion resistance and hydrogen resistance of the cladding layer are improved.

[0033] Example 3 The preparation method of the high-entropy alloy flux-cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90%, ultrasonic cleaning is carried out for 5 min, and the frequency is 35 kHz.

[0034] Step 2: Weigh the following components by mass percentage: Co: 10%, Cr: 20%, Ni: 15%, Al: 20%, Mn: 34%, La2O3: 1%, and the sum of the mass percentages of the above components is 100%; Step 3: Put the mixed powder prepared in Step 2 into a mixer for dry mixing. After the powder is fully mixed, put the powder into a drying oven for drying at a temperature of 150 °C for 30 min. After drying, the flux-cored powder is obtained; Step 4: Wrap the flux-cored powder obtained in Step 3 in a FeCoNi strip by a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm; Step 5: Carry out multi-pass cold drawing and reducing through a wire drawing die on the flux-cored wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm; wipe the oil stain on the wire with a cotton cloth dipped in anhydrous ethanol or acetone, and finally straighten the wire through a wire drawing machine, coil it into a disc, and seal it for packaging.

[0035] The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: successively pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

[0036] The welding process of the high-entropy alloy flux-cored wire prepared in Example 3 is: tungsten inert gas shielded welding (TIG), the welding current is 130 A, the voltage is 15 - 20 V, the welding speed is 0.15 m / min, and the shielding gas is pure argon. When using this wire for welding, the arc is stable, the weld formation is beautiful, and there are no defects such as pores, inclusions, cracks, and oxidation. The microhardness of the obtained high-entropy alloy coating reaches 536 HV 0.5 , and the corrosion current density of the cladding layer is 1.20×10 -4 A·cm -2 , and the hydrogen diffusion coefficient is 2.03×10 -6 cm 2 / s. Compared with the corrosion current density of the base material of the hydrogen storage tank body, it is lower, and the hydrogen diffusion coefficient is smaller (the corrosion current density of the base material is 1.6×10 -4 A·cm -2 and the hydrogen diffusion coefficient is 2.98×10 -6 cm 2 / s). The corrosion resistance and hydrogen resistance of the cladding layer are improved.

[0037] Example 4 The preparation method of the high-entropy alloy flux-cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90%, ultrasonic cleaning is carried out for 5 min, and the frequency is 35 kHz.

[0038] Step 2: Weigh the following components by mass percentage: Co: 10%, Cr: 20%, Ni: 15%, Al: 20%, Mn: 30%, La2O3: 5%, and the sum of the mass percentages of the above components is 100%; Step 3: Put the mixed powder prepared in Step 2 into a mixer for dry mixing. After the powder is fully mixed, put the powder into a drying oven for drying at a temperature of 150 °C for 30 min. After drying, the flux-cored powder is obtained; Step 4: Wrap the flux-cored powder obtained in Step 3 around the FeCoNi strip by a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm; Step 5: Carry out multi-pass cold drawing and reducing through a wire drawing die on the high-entropy alloy flux-cored wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm; wipe the oil stains on the wire with a cotton cloth dipped in anhydrous ethanol or acetone, and finally straighten the wire through a wire drawing machine, coil it into a disk, and seal and package it.

[0039] The welding process of the high-entropy alloy flux-cored wire prepared in Example 4 is: tungsten inert gas shielded welding (TIG), the welding current is 130 A, the voltage is 15 - 20 V, the welding speed is 0.15 m / min, and the shielding gas is selected as pure argon. When using this wire for welding, the arc is stable, the weld formation is beautiful, and there are no defects such as pores, inclusions, cracks, and oxidation. The microhardness of the obtained high-entropy alloy coating reaches 558 HV 0.5 , the corrosion current density of the cladding layer is 1.05×10 -4 A·cm -2 , the hydrogen diffusion coefficient is 1.87×10 -6 cm 2 / s, which is lower than the corrosion current density of the base material of the hydrogen storage tank body and smaller in hydrogen diffusion coefficient (the corrosion current density of the base material is 1.6×10 -4 A·cm -2 and the hydrogen diffusion coefficient is 2.98×10 -6 cm 2 / s). The corrosion resistance and hydrogen resistance of the cladding layer are improved. Observe the metallographic structure of the obtained cladding layer (such as Figure 1 , Figure 2 , Figure 3As shown in the figure, they are the lower and upper parts of the coating respectively. It can be seen from the figure that the lower part of the coating is mainly composed of columnar crystals with a small amount of equiaxed crystals; the upper part of the coating is composed of fine and uniform cellular crystals and equiaxed crystals, and the bonding between the coating and the substrate is good.

[0040] Example 5 The preparation method of the high-entropy alloy flux-cored wire of the present invention is specifically implemented according to the following steps: Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 95%, the ultrasonic cleaning time is 8 min, and the frequency is 40 kHz.

[0041] Step 2: Weigh the following components by mass percentage: Co: 10%, Cr: 15%, Ni: 15%, Al: 28%, Mn: 28%, La2O3: 4%, and the sum of the mass percentages of the above components is 100%; Step 3: Put the powder in Step 2 into a mixer for dry mixing. After the powder is fully mixed, dry it at a drying temperature of 200 °C for 25 min to obtain the flux powder; Step 4: Wrap the flux powder obtained in Step 3 inside the FeCoNi strip through a flux-cored wire making machine, and use a forming machine to close the FeCoNi strip to obtain a wire precursor with a diameter of 2.1 mm; Step 5: Perform multi-pass cold drawing and reducing through a wire drawing die on the wire precursor obtained in Step 4 to obtain a wire with a diameter of 1.42 mm. Finally, wipe the oil stains on the wire with a cotton cloth dipped in anhydrous ethanol or acetone, and finally straighten the wire through a wire drawing machine, coil it into a disk, and seal it for packaging to obtain the high-entropy alloy flux-cored wire; The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: successively pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

[0042] Example 6 Step 1: Ultrasonically clean the FeCoNi strip with an ethanol solution to obtain a clean FeCoNi strip; The mass fraction of the ethanol solution is 90 - 95%, the ultrasonic cleaning time is 5 - 8 min, and the frequency is 35 - 40 kHz.

[0043] Step 2: Weigh the following components by mass percentage: Co: 8%, Cr: 18%, Ni: 10%, Al: 30%, Mn: 30%, La2O3: 4%, and the sum of the mass percentages of the above components is 100%; Step 3: Put the powder obtained in Step 2 into a mixer for dry mixing. After the powder is fully mixed, conduct drying at a temperature of 150 °C for 30 minutes to obtain the flux-cored powder. Step 4: Wrap the flux-cored powder obtained in Step 3 inside a FeCoNi strip using a flux-cored wire making machine, and close the FeCoNi strip using a forming machine to obtain a wire precursor with a diameter of 2.1 mm. Step 5: Subject the wire precursor obtained in Step 4 to multi-pass cold drawing and reducing through a wire drawing die to obtain a wire with a diameter of 1.42 mm. Finally, wipe the oil stains on the wire with a cotton cloth dipped in anhydrous ethanol or acetone. Finally, straighten the wire through a wire drawing machine, coil it into a disk, and perform sealed packaging to obtain the high-entropy alloy flux-cored wire. The specific process of the multi-pass cold drawing and reducing wire drawing die is as follows: sequentially pass through wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm.

Claims

1. High entropy alloy flux-cored welding wire, characterized in that: The invention comprises a flux core and a welding skin, wherein the flux core is composed of the following components by mass percentage: Co: 5%-10%, Cr: 10%-20%, Ni: 10%-15%, Al: 20%-30%, Mn: 15%-35%, La2O3: 1%-5%, and the sum of the mass percentages of the above components is 100%.

2. The high entropy alloy flux-cored welding wire according to claim 1, characterized in that: The welding skin is a FeCoNi strip, and the welding skin is composed of the following components by mass percentage Composition: Cr: 0.005%, Cu: 0.015%, Si: 0.2%, Mn: 0.26%, Co: 17.50%, Ni: 30.0%, Fe is the balance, and the sum of the mass percentages of the above components is 100%.

3. The high entropy alloy flux-cored welding wire according to claim 1, characterized in that: The filling rate of the drug core is 30wt%~40wt%.

4. A method for preparing a high entropy alloy flux-cored welding wire, characterized in that: Follow the steps below to implement it: Step 1: Ultrasonic cleaning of the FeCoNi tape using an ethanol solution; Step 2: Weigh the following components by mass percentage: Co: 5%~10%, Cr: 10%~20%, Ni: 10%~15%, Al: 20%~30%, Mn: 15%~35%, La2O3: 1%~5%, and the sum of the mass percentages of the above components is 100%; Step 3: Put the powder from step 2 into a mixer for dry mixing and drying to obtain core powder; Step 4: wrapping the flux core powder obtained in step 3 in a FeCoNi belt through a flux cored welding wire making machine, and closing the FeCoNi belt with a forming machine to obtain a welding wire precursor; Step 5: The welding wire precursor obtained in step 4 is subjected to multiple cold drawing and diameter reduction drawing dies to obtain a welding wire with a diameter of 1.42 mm. The oil stains on the welding wire are wiped off with cotton cloth. Finally, the welding wire is straightened by a wire drawing machine, coiled into a disc, and sealed and packaged to obtain a high entropy alloy flux-cored welding wire.

5. The method for preparing a high entropy alloy flux-cored welding wire according to claim 4, characterized in that: In the step 1, the mass fraction of the ethanol solution is 90-95%, the ultrasonic cleaning time is 5-8 minutes, and the frequency is 35-40kHz.

6. The method for preparing a high entropy alloy flux-cored welding wire according to claim 4, characterized in that: In step 5, the specific process of the multi-pass cold drawing and reducing wire drawing die is: passing through the wire drawing dies with diameters of 1.9 mm, 1.7 mm, 1.5 mm, and 1.42 mm in sequence.

7. A method for preparing a hydrogen embrittlement resistant high entropy alloy coating using the high entropy alloy flux-cored welding wire according to any one of claims 1 to 6, characterized in that: Specifically, a high entropy alloy flux-cored wire is clad on the inner surface of the hydrogen storage tank using TIG welding cladding.

8. The method for preparing a hydrogen embrittlement resistant high entropy alloy coating using a high entropy alloy flux-cored welding wire as claimed in claim 7, characterized in that: The welding current is 120A~140A, the cladding speed is 0.10m / min~0.20m / min, argon gas is introduced for protection during cladding, the welding method is double-layer multi-pass welding, and the weld overlap rate during the cladding process is 30%-40%.

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