Method and device for purifying amorphous alloy return material by using pulse electric field

Abstract

The present application relates to a kind of with pulse electric field to amorphous alloy return material clean smelting method and device, belong to alloy melt purification technical field, it is a kind of low energy consumption, low emission high-efficiency industrial amorphous alloy master alloy smelting impurity removal technology;The method is based on the electric free energy driving theory, by specific device in the melt side bottom setting positive and negative electrode source, generate from horizontal direction to vertical direction in melt multi-angle current density distribution, rely on current density gradient driving force to make the inclusion in melt along the current density gradient direction migration to melt far from the electrode area and melt top, realize the purpose of purifying amorphous alloy melt.The technical scheme provided by the present application is applicable to the process of amorphous alloy return material impurity removal.

Description

Technical Field

[0001] This invention relates to the field of alloy melt purification technology, and in particular to a method and apparatus for purifying and smelting amorphous alloy return materials using a pulsed electric field. Background Technology

[0002] Zirconium-based amorphous alloys, due to their high strength, high hardness, strong corrosion resistance, wear resistance, and superplasticity within a certain temperature range, have been widely used in consumer electronics, biomedicine, and precision machinery, and are considered among the most promising new structural materials. As users' demands for the quality of amorphous alloy products continue to increase, higher requirements are being placed on the material's performance and purity. The Zr element in zirconium-based amorphous alloys is chemically unstable and readily combines with oxygen; therefore, zirconium-based amorphous alloys need to be smelted in a vacuum environment. However, because the raw materials contain a certain amount of oxygen, ZrO2 is formed during the smelting process. Furthermore, to reduce the oxygen content in the amorphous alloy, rare earth deoxidizers are usually added during the smelting process, resulting in the formation of rare earth oxides. Non-metallic inclusions in zirconium-based amorphous alloys, especially oxide inclusions introduced by deoxidizers, have a significant impact on their material properties and service life.

[0003] Inclusions in zirconium-based amorphous alloys (Zr-Cu-Ni-Al-Nb-Y) mainly include ZrO2, Al2O3, and Y2O3. These inclusions exist either singly or in aggregate form within the matrix. These hard non-metallic inclusions are particularly prone to causing stress concentration, leading to cracks and fatigue failure, thus affecting the performance of the amorphous alloy. Therefore, these non-metallic inclusions have become the main culprit for the deterioration of amorphous alloy materials. Reducing the content of non-metallic inclusions in amorphous alloys is therefore of great significance for improving their service performance.

[0004] The core of improving the cleanliness of amorphous alloys lies in smelting. The degree of cleanliness in the smelting process determines the quality of downstream products, and high-purity master alloys are the foundation for preparing high-performance service materials. Therefore, the research and development of industrial amorphous alloy smelting and purification processes is particularly important! Chinese patent CN113462994B discloses a vacuum melting process for removing matrix oxide impurities from zirconium-based amorphous alloys. This method mainly involves vacuum melting the zirconium-based amorphous alloy in a furnace, introducing inert gas into the furnace, feeding calcium wire into the melt and stirring the melt, allowing calcium to undergo a redox reaction with the matrix oxide impurities to form CaO. After standing for a certain period of time, the CaO is removed after floating to the surface. This method not only requires the addition of extra calcium wire, increasing the process flow and smelting costs, but also increases smelting time and reduces production efficiency. Chinese patent CN113528986B discloses an ultra-high toughness large-size zirconium-based amorphous alloy, its preparation method, and its applications. This method utilizes a specific ratio of Zr, Cu, Ni, and Al to prepare the zirconium-based amorphous alloy. By limiting the content of each component in the Zr-Cu-Ni-Al system, the amorphous alloy possesses ultra-high toughness, high glass-forming ability, and good repeatability, resolving the contradiction that current zirconium-based amorphous alloys cannot simultaneously possess good glass-forming ability and bending resistance. However, this method is complex and energy-intensive, which does not meet the requirements of current industrial green development plans. Chinese patent CN106319273B discloses a melt purification salt and a melt purification treatment method for improving the forming ability of aluminum-based amorphous alloys. This method involves adding an additional molten salt, CaF2, to a basic molten salt system KCl-MgCl2-CaCl2. The amount of CaF2 added is 10-30% of the total weight of the basic molten salt system. When purifying the aluminum-based amorphous alloy melt, the amount of the added molten salt is 0.5-2% of the total weight of the aluminum-based amorphous alloy. However, this method requires the addition of extra molten salt, increasing smelting costs, and its effect on refining the grain size of the aluminum-based amorphous master alloy is limited.

[0005] It is evident that existing traditional processes such as vacuum induction melting, electric arc melting, electron beam melting, Ca treatment, and ceramic filtration are no longer sufficient to meet the requirements of various fields for amorphous alloys with higher purity.

[0006] Therefore, it is necessary to study a new method and apparatus for the clean smelting of amorphous alloy return materials using pulsed electric fields to address the shortcomings of existing technologies and to solve or mitigate one or more of the aforementioned problems. Summary of the Invention

[0007] In view of this, the present invention provides a method and apparatus for purifying and smelting amorphous alloy return materials using a pulsed electric field, which is a low-energy-consumption, low-emission, and highly efficient industrial amorphous alloy master alloy smelting and impurity removal technology.

[0008] On one hand, the present invention provides an apparatus for purifying and smelting amorphous alloy return material using a pulsed electric field. The apparatus includes: a pulsed power supply, a positive electrode, a negative electrode, two corundum sleeves, two sets of wires, two sets of clamps, a crucible, and a melt.

[0009] The melt is placed in the crucible;

[0010] The upper sections of the positive electrode and the negative electrode are disposed inside the corresponding corundum sleeves, and the lower sections protrude from the corundum sleeves; the positive electrode and the negative electrode are respectively inserted on both sides of the same end of the melt; the corundum sleeves are fixed to the side wall of the crucible by the clamps;

[0011] The positive electrode and the negative electrode are respectively connected to the positive and negative terminals of the pulse power supply through corresponding wires.

[0012] In addition to the aspects described above and any possible implementation, a further implementation is provided in which the lower section lengths of the positive electrode and the negative electrode are 1 / 4 to 1 / 3 of the melt depth.

[0013] In addition to the aspects described above and any possible implementations, a further implementation is provided in which the distance between the bottom of the corundum sleeve and the bottom of the crucible is 1 / 4 to 1 / 3 of the melt depth.

[0014] In addition to the aspects and any possible implementations described above, a further implementation is provided in which the positive electrode and the negative electrode are made of pure iron, pure nickel or pure molybdenum and are rod-shaped.

[0015] In addition to the aspects and any possible implementations described above, a further implementation is provided in which the diameter of both the positive electrode and the negative electrode is 5-15 mm and the length is 30-300 mm.

[0016] In addition to the aspects and any possible implementations described above, a further implementation is provided in which the wire is made of pure molybdenum and the clamp is made of stainless steel.

[0017] On the other hand, the present invention provides a method for purifying and smelting amorphous alloy return material using a pulsed electric field, wherein the method is implemented using any of the devices described above;

[0018] The steps of the method include:

[0019] S1. Dry the zirconium-based amorphous alloy return material to remove the moisture on the surface of the return material, and place the crucible in a drying furnace for drying. Then, evenly place the small pieces of return material in the crucible and place the crucible in a vacuum furnace.

[0020] S2. Insert a set of electrodes into both sides of the crucible and cover them with corundum sleeves, ensuring that a certain length is left at the bottom of the electrodes; fix the corundum sleeves to the crucible with clamps, and connect the electrodes to the external pulse power supply with wires.

[0021] S3. Start the vacuum pump to evacuate the vacuum furnace to remove oxygen from the furnace and introduce argon atmosphere into the furnace; then start the heating device to raise the temperature inside the furnace to above 1200℃ and keep it at that temperature for more than 30 minutes to completely melt the return material in the crucible.

[0022] S4. Start the pulse power supply to generate a multi-angle current density gradient field from the horizontal to the vertical direction in the melt, driving non-metallic inclusions to migrate to the far electrode and the top region of the melt for purification treatment; after the preset purification treatment time, start cooling, and turn off the pulse power supply to stop the purification treatment when the furnace temperature drops to 400℃.

[0023] In addition to the aspects described above and any possible implementation, a further implementation is provided in which the length of the electrode in step S2 is 1 / 4 to 1 / 3 of the melt depth; and the distance between the bottom end of the corundum sleeve and the bottom of the crucible is 1 / 4 to 1 / 3 of the melt depth.

[0024] In addition to the aspects and any possible implementations described above, a further implementation is provided in which the non-metallic inclusions include any one or more of Y2O3, Al2O3, and ZrO2, and the size of the non-metallic inclusions ranges from 0.5 to 30 μm.

[0025] In addition to the aspects and any possible implementations described above, a further implementation is provided in which the parameters of the purification process in step S4 are: pulse current intensity of 10A-500A, frequency of 100Hz-10000Hz, and pulse width of 1μs-10ms.

[0026] Compared with the prior art, one of the above technical solutions has the following advantages or beneficial effects: Compared with the existing amorphous alloy purification and smelting technology in industry, the present invention does not require the addition of additional additives, which can reduce production costs;

[0027] Another technical solution in the above technical solution has the following advantages or beneficial effects: The present invention is based on the theory of electric free energy driving. A positive and negative electrode source is set at the bottom of one side of the melt through a specific device. A multi-angle current density distribution from the horizontal direction to the vertical direction is generated in the melt. The inclusions in the melt are driven by the current density gradient to migrate along the current density gradient direction to the area of ​​the melt away from the electrode and the top of the melt, thereby achieving the purpose of purifying the amorphous alloy melt.

[0028] Another technical solution in the above technical solution has the following advantages or beneficial effects: The pulse power supply used in this invention is intermittent discharge, and its energy consumption is comparable to that of ordinary fluorescent lamps. In addition, this invention also has the advantages of convenient operation and green energy saving, which helps to improve the efficiency of metal smelting and realize the pollution-free, emission-free, low-energy-consumption, low-cost, high-efficiency production and large-scale application of high-quality amorphous alloy materials.

[0029] Another technical solution in the above-mentioned technical solution has the following advantages or beneficial effects: The present invention sets two electrodes at the same end of the melt, thereby generating a non-uniform electric field with a current density gradient from the near electrode end to the far electrode end on the horizontal plane; if the electrodes are set at both ends, only a uniform electric field will be generated on the horizontal plane; the current density difference on both sides of the inclusion in the non-uniform electric field will be two orders of magnitude higher than the current density difference on both sides of the inclusion in the uniform electric field, and the inclusion can obtain a greater driving force, which is more conducive to purifying the melt;

[0030] Another technical solution in the above-mentioned technical solution has the following advantages or beneficial effects: the way the bottom of the electrode of the present invention is set with a portion exposed can generate a non-uniform electric field not only in the horizontal plane, but also in the vertical plane, and in the region between the vertical and horizontal planes. It can generate more directions and greater driving force on the inclusions.

[0031] Of course, any product implementing this invention does not necessarily need to achieve all of the technical effects described above at the same time. Attached Figure Description

[0032] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 This is a schematic diagram of a device for purifying and smelting amorphous alloy return material using a pulsed electric field, according to an embodiment of the present invention.

[0034] Figure 2 These are scanning electron microscope (SEM) images of the ingot from the electrode position in Embodiment 1 of the present invention at near, middle and far distances, with (a) being the near electrode end, (b) being the middle region and (c) being the far electrode end.

[0035] Figure 3 These are scanning electron microscope (SEM) images of the upper, middle, and lower parts of the middle region of the ingot in Embodiment 3 of the present invention, with (a) representing the upper part, (b) representing the middle part, and (c) representing the bottom part.

[0036] In the figure:

[0037] 1. Pulse power supply; 2. Electrode; 3. Corundum sleeve; 4. Wire; 5. Fixture; 6. Melt; 7. Crucible; 8. Vertical current line; 9. Horizontal current line. Detailed Implementation

[0038] To better understand the technical solution of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0039] It should be understood that the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0040] In order to overcome the above-mentioned problems in the prior art, the present invention provides a method and apparatus for purifying and smelting amorphous alloy return material using a pulsed electric field. This method can drive the directional migration of non-metallic inclusions in the amorphous alloy melt by applying a multi-angle current density gradient to the amorphous alloy melt, thereby achieving the purpose of purifying and smelting the amorphous alloy melt.

[0041] The present invention provides a method for purifying and smelting amorphous alloy return material using a pulsed electric field. This method involves placing a pair of positive and negative electrode rods at one end of the amorphous alloy melt, using a corundum tube to cover the electrode rods, fixing the corundum tube with a clamp, and maintaining a preset length at the bottom of the electrode rods to contact the amorphous alloy melt. This generates a multi-angle current density gradient within the melt, driving non-metallic inclusions within the melt to migrate directionally to the far electrode end and the upper surface of the melt, thereby purifying the amorphous alloy melt.

[0042] like Figure 1 As shown, the device of the present invention includes a pulse power supply 1, electrodes 2, a corundum sleeve 3, wires 4, a clamp 5, a crucible 7, and a melt 6. The melt 6 is placed inside the crucible 7. The bottom ends of both positive and negative electrodes 2 are inserted into the melt 6. A corundum sleeve 3 is fitted around the outer periphery of the electrodes 2. The corundum sleeve 3 is clamped and fixed to the crucible by the clamp 5, which is fixedly connected to the side wall of the crucible 7. The wires 4 connect the electrodes 2 and the pulse power supply 1. The entire crucible is placed inside a vacuum furnace.

[0043] In this invention, electrode 2 is inserted into a corundum sleeve 3, with the bottom of the electrode protruding beyond the sleeve 3 by 10-20 mm, corresponding to a melt height of approximately 40-60 mm. This means the exposed length of the electrode is 1 / 4 to 1 / 3 of the melt depth. The bottom of the corundum sleeve 3 is sealed to the outer periphery of the electrode 2. Specifically, the inner diameter of the corundum sleeve 3 must be equal to the diameter of the electrode 2 to ensure close contact between the bottom of the corundum sleeve 3 and the periphery of the electrode 2. The corundum sleeve 3 is clamped and fixed to the side wall of the crucible 7 by a clamp 5, ensuring that the bottom of the corundum sleeve 3 always maintains a certain distance from the bottom of the crucible 7, preferably 1 / 4 to 1 / 3 of the melt depth. After insertion, the 10-20 cm exposed length of electrode 2 ensures that the exposed length of electrode 2 is 1 / 4 to 1 / 3 of the melt depth. By combining electrode 2 with corundum sleeve 3, only the bottom 10-20mm of electrode 2 contacts the melt, generating a multi-angle current density gradient field from horizontal current line 9 to vertical current line 8 in the melt, driving inclusions to migrate to the far electrode and top region, thus achieving regional purification of the amorphous alloy melt.

[0044] Preferably, the electrode 2 used in this invention is made of pure iron, pure nickel or pure molybdenum, and is rod-shaped with a diameter of 5-15 mm and a length of 30-300 mm.

[0045] Preferably, the conductor 4 used in this invention is made of pure molybdenum, and the clamp is made of stainless steel.

[0046] Preferably, the non-metallic inclusions in the melt 6 of the present invention include any one or more of Y2O3, Al2O3, and ZrO2, and the size range of the non-metallic inclusions is between 0.5 and 30 μm.

[0047] Preferably, the present invention also provides a method for purifying non-metallic inclusions in continuously cast billets, the method being implemented using the aforementioned apparatus, and specifically comprising the following steps:

[0048] Step 1: Dry the zirconium-based amorphous alloy return material to remove moisture from the surface of the return material. Place the corundum crucible in a drying furnace for drying treatment, and then evenly place the small pieces of return material in the rectangular corundum crucible.

[0049] Step 2: Insert a set of electrode rods into one side of the corundum crucible and cover them with corundum sleeves. Fix the corundum sleeves with clamps and ensure that the bottom of the electrode rods is 10-20mm long. Connect the electrode rods to the external pulse power supply with wires. When connecting, the wires pass through the preset connection ports on the vacuum furnace to achieve the connection between the inside and outside of the vacuum furnace.

[0050] Step 3: Start the vacuum pump to evacuate the vacuum furnace chamber to remove oxygen from the furnace, and then introduce an argon atmosphere into the furnace; then start the heating device to raise the temperature inside the furnace to above 1200℃ and hold it for 30 minutes to completely melt the amorphous alloy in the crucible.

[0051] Step 4: Set parameters such as pulse frequency, pulse width, input current, and input voltage. Start the pulse power supply to generate a pulse electric field. After the pulse processing time is preset, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0052] The pulse current intensity is set to 10A-500A, the frequency to 100Hz-10000Hz, the pulse width to 1μs-10ms, and the pulse processing time to 0.1-24h.

[0053] Example 1:

[0054] This embodiment applies a pulsed electric field to drive the directional movement of non-metallic inclusions during the vacuum melting process of zirconium-based amorphous alloy (Zr-Cu-Ni-Al-Nb-Y), thereby improving the material cleanliness. The specific steps are as follows:

[0055] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0056] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0057] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0058] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 1000Hz, the pulse current is 100A, and the pulse width is 200μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0059] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0060] Example 2:

[0061] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0062] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0063] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0064] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 2000Hz, the pulse current is 120A, and the pulse width is 150μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0065] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0066] Example 3:

[0067] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0068] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0069] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0070] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 5000Hz, the pulse current is 140A, and the pulse width is 100μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0071] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0072] Example 4:

[0073] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0074] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0075] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0076] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 10000Hz, the pulse current is 150A, and the pulse width is 50μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0077] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0078] Example 5:

[0079] Step 1: Place 1000g of zirconium-based amorphous alloy return material in a drying oven and dry at 180℃ for 30 minutes. Place the corundum crucible in a heating furnace and preheat at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0080] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0081] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0082] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 10000Hz, the pulse current is 150A, and the pulse width is 50μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0083] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0084] Example 6: (Blank Sample)

[0085] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0086] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 10mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0087] Step 3: Start the vacuum pump to evacuate the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 40 minutes.

[0088] Step 4: Stop heating and begin cooling. Wait until the furnace temperature drops to 400℃ to allow the amorphous alloy to solidify completely.

[0089] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0090] Example 7:

[0091] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0092] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 30mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0093] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0094] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 5000Hz, the pulse current is 140A, and the pulse width is 100μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0095] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0096] Example 8:

[0097] Step 1: Place 500g of zirconium-based amorphous alloy return material in a drying oven at 180℃ for 30 minutes, and preheat the corundum crucible in a heating furnace at 400℃ for 2 hours. Place the dried zirconium-based amorphous alloy return material into the preheated corundum crucible.

[0098] Step 2: Insert two pure nickel electrode rods into one side of the corundum crucible and cover them with corundum tubes. Install the stainless steel clamp on the side wall of the crucible and fix the corundum tubes, ensuring that the bottom of the electrode rods is 50mm away. Connect the pure nickel wires to the pure nickel electrode rods and connect them to the external pulse power supply through the preset connection port of the vacuum furnace.

[0099] Step 3: Start the vacuum pump to evacuate the oxygen in the vacuum furnace and introduce an argon atmosphere. Start the vacuum furnace and heat it to 1200℃ to completely melt the amorphous alloy and hold it at that temperature for 30 minutes.

[0100] Step 4: Set the pulse power supply parameters and start the pulse power supply. The frequency is 5000Hz, the pulse current is 140A, and the pulse width is 100μs. After pulse processing for 10 minutes, stop heating and start cooling. After the furnace temperature drops to 400℃ and the amorphous alloy is completely solidified, turn off the pulse power supply.

[0101] Step 5: Remove the zirconium-based amorphous alloy ingot. Using wire cutting, divide the ingot into three parts along the perpendicular bisector of the two electrodes: the area near the electrodes, the middle area, and the area away from the electrodes. Take 5×5×5mm samples from the top, bottom, and middle of each of these three areas. 3 Three cubes were ground and polished, and then an automatic inclusion analysis was performed using a field emission scanning electron microscope to count inclusions larger than 0.5 μm in size within each square millimeter of the sample.

[0102] In Examples 3, 7, and 8, the exposed electrode lengths were 10 mm, 30 mm, and 50 mm, respectively, and the melt depth was 50 mm. The results are shown in Table 2. When the exposed electrode length was 10 mm, the average number density of inclusions was lowest near the bottom of the electrode region. The number density increased from the near electrode end to the far electrode end and from the bottom to the top, forming a radial purification space from the bottom of the near electrode end to the top of the far electrode end. This is attributed to the effect of the multi-angle current density gradient field (horizontal to vertical range). Compared to a uniform electric field, the multi-angle current density gradient field has a greater driving force, thus purifying inclusions more efficiently. Simultaneously, the multi-angle current density gradient field can expand the purification area.

[0103] Table 1 Comparison of sample mass, power parameters, and quantity density in the examples.

[0104]

[0105]

[0106] Table 2 Comparison of electrode insertion depth and number density near the electrode cross section in the examples.

[0107]

[0108] The foregoing has provided a detailed description of a method and apparatus for the clean smelting of amorphous alloy return materials using a pulsed electric field, as provided in the embodiments of this application. The descriptions of the embodiments above are merely for the purpose of helping to understand the method and its core ideas; furthermore, those skilled in the art will recognize that, based on the ideas of this application, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this application.

[0109] It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a product or system comprising a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a product or system. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the product or system including said element. "Substantially" means within an acceptable margin of error, indicating that a person skilled in the art can resolve the technical problem and substantially achieve the technical effect within a certain margin of error.

[0110] The terminology used in the embodiments of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms “a,” “the,” and “the” used in the embodiments of this invention and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. The term “and / or” as used herein is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, and B alone. Additionally, the character “ / ” in this document generally indicates that the preceding and following related objects are in an “or” relationship.

Claims

1. An apparatus for the clean smelting of amorphous alloy return materials using a pulsed electric field, characterized in that, The device includes: a pulse power supply, a positive electrode, a negative electrode, two corundum sleeves, two sets of wires, two sets of clamps, a crucible, and a melt; The melt is placed in the crucible; The upper sections of the positive electrode and the negative electrode are disposed inside the corresponding corundum sleeves, and the lower sections protrude from the corundum sleeves; the positive electrode and the negative electrode are respectively inserted on both sides of the same end of the melt; the corundum sleeves are fixed to the side wall of the crucible by the clamps; The positive electrode and the negative electrode are respectively connected to the positive and negative terminals of the pulse power supply through corresponding wires.

2. The device for purifying and smelting non-crystalline alloy return material using an impulse electric field according to claim 1, characterized in that, The length of the lower section of the positive electrode and the negative electrode is 1 / 4 to 1 / 3 of the melt depth.

3. The device for purifying and smelting non-crystalline alloy return material using an impulse electric field according to claim 1, characterized in that, The distance between the bottom of the corundum sleeve and the bottom of the crucible is 1 / 4 to 1 / 3 of the melt depth.

4. The apparatus for clean smelting of amorphous alloy return material using pulsed electric field according to claim 1, characterized in that, The positive electrode and the negative electrode are made of pure iron, pure nickel or pure molybdenum, and are rod-shaped.

5. The apparatus for clean smelting of amorphous alloy return material using pulsed electric field according to claim 1, characterized in that, The diameter of both the positive electrode and the negative electrode is 5-15 mm, and the length is 30-300 mm.

6. The apparatus for clean smelting of amorphous alloy return material using pulsed electric field according to claim 1, wherein The conductor is made of pure molybdenum, and the clamp is made of stainless steel.

7. A method for purifying and smelting amorphous alloy return material using a pulsed electric field, characterized by, The method is implemented using the apparatus described in any one of claims 1-6; The steps of the method include: S1. Dry the zirconium-based amorphous alloy return material to remove the moisture on the surface of the return material, and place the crucible in a drying furnace for drying. Then, evenly place the small pieces of return material in the crucible and place the crucible in a vacuum furnace. S2. Insert a set of electrodes into both sides of the crucible and cover them with corundum sleeves, ensuring that a certain length is left at the bottom of the electrodes; fix the corundum sleeves to the crucible with clamps, and connect the electrodes to the external pulse power supply with wires. S3. Start the vacuum pump to evacuate the vacuum furnace to remove oxygen from the furnace and introduce argon atmosphere into the furnace; then start the heating device to raise the temperature inside the furnace to above 1200℃ and keep it at that temperature for more than 30 minutes to completely melt the return material in the crucible. S4. Start the pulse power supply to generate a multi-angle current density gradient field from the horizontal to the vertical direction in the melt, driving the non-metallic inclusions to migrate to the far-end electrode and the top area of ​​the melt for purification. After the preset purification time, the temperature begins to drop. Once the furnace temperature drops to 400℃, the pulse power supply is turned off, and the purification process is stopped.

8. The method of claim 7, wherein the method is characterized by: In step S2, the length of the electrode is 1 / 4 to 1 / 3 of the melt depth; the distance between the bottom of the corundum sleeve and the bottom of the crucible is 1 / 4 to 1 / 3 of the melt depth.

9. The method for purifying and smelting amorphous alloy return material using a pulsed electric field according to claim 7, characterized in that, The non-metallic inclusions include any one or more of Y2O3, Al2O3, and ZrO2, and the size of the non-metallic inclusions ranges from 0.5 to 30 μm.

10. The method for purifying and smelting amorphous alloy return material using a pulsed electric field according to claim 7, characterized in that, The parameters for purification in step S4 are: pulse current intensity of 10A-500A, frequency of 100Hz-10000Hz, and pulse width of 1μs-10ms.

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