Zirconium-based amorphous purification and smelting apparatus and smelting method

Abstract

This invention provides a zirconium-based amorphous alloy purification and melting apparatus, adapted for use with a vacuum melting furnace, comprising a purification mechanism, a power control mechanism, and a purification power supply. The purification mechanism includes a cathode plate, an anode plate, and a purification power supply. The cathode plate is connected to the purification power supply via a cathode connecting line, and the anode plate is connected to the purification power supply via an anode connecting line. This invention also provides a purification and melting method. Using the above-mentioned equipment for purification and melting, the oxide impurity content of the zirconium-based amorphous master alloy ingot treated by the melting method provided in this invention is significantly reduced. The zirconium-based amorphous products die-cast from this master alloy exhibit more stable performance and better mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of alloy smelting technology, specifically relating to a zirconium-based amorphous purification smelting device and smelting method. Background Technology

[0002] Zirconium-based amorphous alloys are currently the most commonly used formulation in commercial bulk amorphous alloys. In actual production of zirconium-based amorphous master alloys, sponge zirconium is generally used as the zirconium source material. However, commercially available sponge zirconium has a relatively high oxygen content. Using amorphous master alloy ingots made from high-oxygen raw materials results in subsequent zirconium-based amorphous products with equally high oxygen content, thus affecting product performance, increasing microscopic defects, brittleness, and breakage. To address the problem of excessively high oxygen content in sponge zirconium raw materials, existing technologies typically improve this during the smelting process. This involves adding trace amounts of rare earth elements, such as yttrium and lanthanum, to the molten zirconium-based amorphous alloy during smelting. These elements react directly with oxygen in the melt to form insoluble oxides (such as yttrium oxide). These oxide impurities float on the surface of the melt, and the oxide scale on the surface of the master alloy ingot is removed after cooling.

[0003] The addition of deoxidizers in existing technologies has been a long-standing practice, but it is somewhat insufficient for the smelting and production of zirconium-based amorphous alloys. This is because the oxide slag generated during the smelting process, such as yttrium oxide, typically consists of particles ranging from 5 to 100 μm in size suspended in the alloy melt. Only a sufficient quantity of slag has enough buoyancy to float to the melt surface; the oxide slag that cannot reach the surface remains suspended in the melt as particles and cannot be removed. These non-floating oxide particles have a density very close to that of the molten zirconium-based amorphous alloy, making it difficult to separate them from the melt using traditional slag removal methods such as physical slag skimming. The residual oxide particle impurities form heterogeneous points in the zirconium-based amorphous master alloy, creating mechanically weak points after processing into amorphous products, leading to decreased performance and increased susceptibility to breakage. Summary of the Invention

[0004] The purpose of this invention is to provide a zirconium-based amorphous purification and smelting apparatus and a phase-adapted smelting method suitable for removing impurities from zirconium-based amorphous materials, aiming to solve the technical problem that slag cannot be completely removed after slag removal during the zirconium-based amorphous smelting process.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0006] This invention provides a zirconium-based amorphous purification and melting device, which is compatible with a vacuum melting furnace and includes a purification mechanism, a power control mechanism, and a purification power supply.

[0007] The purification mechanism includes a cathode plate, an anode plate, and a purification power supply. The cathode plate is connected to the purification power supply via a cathode connection line, and the anode plate is connected to the purification power supply via an anode connection line.

[0008] The cathode plate is a graphite plate, and the anode plate is a high-temperature alloy plate;

[0009] The cathode plate and the anode plate are arranged opposite to each other and are fixedly connected by an insulating connection part. The insulating connection part is provided with a telescopic rod, which is connected to the power control mechanism. The height of the cathode plate and the anode plate can be adjusted by adjusting the power control mechanism.

[0010] The vacuum melting furnace includes a furnace body and a furnace cover located on top of the furnace body. The top of the furnace cover is opened into a furnace top. The telescopic rod passes through the furnace top and is connected to the power control mechanism outside the melting furnace. The cathode connection line and the anode connection line pass through the furnace top and are connected to the purification power supply outside the melting furnace.

[0011] The zirconium-based amorphous purification and melting device provided by this invention uses an electrochemical method for secondary impurity removal. Research has shown that in the high-temperature molten state, the tiny oxide impurities of zirconium-based amorphous alloys exhibit ionization. Therefore, this invention introduces an external electric field during the refining stage, and the cathode plate adsorbs the extremely fine oxide particles suspended in the melt, thereby achieving the purpose of deep purification of the zirconium-based amorphous melt.

[0012] Preferably, the vacuum melting furnace is equipped with a melting device, which includes a melting crucible and an induction heating coil disposed outside the melting crucible. The induction heating coil is fixedly connected to a rotating handle disposed outside the furnace body through a coil connection part that penetrates the furnace body.

[0013] The lengths of the cathode plate and the anode plate are such that, after extending into the bottom of the crucible, the insulating connection portion remains outside the smelting crucible.

[0014] Both the cathode plate and the anode plate are made of heat-resistant materials. However, since heat-resistant metal materials cannot be used for the insulating connection, the length of the cathode plate and the anode plate is designed so that the insulating connection does not come into contact with the high-temperature molten material and maintains a certain distance to avoid high temperature.

[0015] Preferably, the vacuum melting furnace is equipped with a forming device, which is a copper casting mold, and the copper casting mold is equipped with a sprue and a forming cavity.

[0016] Preferably, the furnace cover is provided with two or more observation windows; the furnace body is provided with air inlet and exhaust outlets. The observation windows are used for direct visual observation of the smelting process and can also be used to place slag removal tools. The air inlet and exhaust outlets on the furnace body are used to connect a vacuum pump and an air intake device for vacuuming, passing inert gas, and exhausting gas.

[0017] The present invention also provides a zirconium-based amorphous purification and melting method adapted to the above-mentioned zirconium-based amorphous purification and melting apparatus, comprising the following steps:

[0018] Place the raw materials to be melted into the melting crucible, close the furnace lid, evacuate the furnace, and fill it with inert gas.

[0019] The induction heating coil is turned on for heating and melting. The cathode plate and anode plate in the pre-melting purification mechanism are located outside the melting crucible.

[0020] After the raw materials are melted evenly, the power control mechanism is operated to drive the telescopic rod to send the cathode plate and anode plate to the bottom of the melting crucible.

[0021] Turn on the purifier power, set the voltage to 6-30V, and the time to 30s-3min;

[0022] After purification, operate the power control mechanism to drive the telescopic rod to lift the cathode plate and anode plate above the melting crucible until no molten liquid drips into the crucible, and then return them to their original positions;

[0023] Turn off the induction heating coil, pour the purified molten liquid into the mold below, and remove it after cooling.

[0024] Preferably, during the heating and melting process, the final temperature of the induction coil is 220-250°C higher than the melting point of the raw material to be melted.

[0025] Preferably, the cathode plate and the anode plate have the same length and the same area when they are arranged opposite each other; the thickness of the cathode plate is 2-3 times that of the anode plate.

[0026] Preferably, the cathode plate and the anode plate are configured as mesh or claw-shaped.

[0027] Preferably, the cathode connecting wire, the anode connecting wire, and the insulating connection portion are wrapped with heat-insulating material.

[0028] The zirconium-based amorphous purification and melting device provided in this invention utilizes an electrochemical method to adsorb and remove tiny suspended oxide impurity particles in the zirconium-based amorphous melt, thereby achieving the purpose of further purifying the zirconium-based amorphous melt.

[0029] The oxide impurity content of the zirconium-based amorphous master alloy ingots treated by the smelting method provided in this invention is significantly reduced, and the zirconium-based amorphous products made by die casting from this master alloy have more stable performance and better mechanical properties. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the structure of a vacuum melting furnace equipped with a zirconium-based purification and melting device in an embodiment of the present invention;

[0031] Figure 2 for Figure 1 Schematic diagram of a zirconium-based purification and smelting unit;

[0032] Figure 3 The metallographic morphology of the zirconium-based amorphous master alloy ingot obtained by vacuum melting in a zirconium-based purification melting device in an embodiment of the present invention is shown under a metallographic microscope (500x).

[0033] Figure 4 The morphology of a zirconium-based amorphous master alloy ingot under a metallographic microscope (500x) without secondary purification treatment;

[0034] Explanation of icon numbers:

[0035] 101. Power control mechanism; 102. Telescopic rod; 103. Furnace top; 104. First observation window; 105. Cathode connection wire; 106. Anode connection wire; 107. Second observation window; 108. Furnace cover; 109. Purified power supply; 110. Cathode plate; 111. Anode plate; 112. Induction heating coil; 113. Melting crucible; 114. Coil connection part; 115. Rotating handle; 116. Furnace body; 117. Inlet; 118. Cavity; 119. Copper mold; 120. Inlet / outlet port; 121. Insulating connection part. Detailed Implementation

[0036] To make the objectives, technical solutions, and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. The embodiments described below are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art in conjunction with the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed; where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0037] In the description of this invention, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0038] In the description of this invention, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0039] Furthermore, unless the context explicitly uses it otherwise, the singular form of a word should be understood as including the plural form of that word. The terms "comprising" or "having" are intended to specify the presence of a feature, quantity, step, operation, element, part, or combination thereof, but are not intended to exclude the presence or possible addition of one or more other features, quantities, steps, operations, elements, parts, or combinations thereof.

[0040] This invention provides a vacuum melting furnace equipped with a zirconium-based amorphous purification and melting device, as shown in the attached schematic diagram. Figure 1 Appendix Figure 2 As shown.

[0041] Specifically, the vacuum furnace equipped with a zirconium-based amorphous purification and melting device includes a purification device, a melting device, and a forming device.

[0042] The purification device includes a purification mechanism, a power control mechanism, and a purification power supply. The purification mechanism includes a cathode plate 110, an anode plate 111, and a purification power supply 109. The cathode plate 110 is connected to the purification power supply 109 via a cathode connection line 105, and the anode plate 111 is connected to the purification power supply 109 via an anode connection line 106.

[0043] In this embodiment, the cathode plate 110 is a graphite plate and the anode plate 111 is a nickel-based high-temperature alloy plate. Both have melting points above the melting point of zirconium-based amorphous materials and do not melt when placed in a zirconium-based amorphous melt.

[0044] In this embodiment, the cathode plate 110 and the anode plate 111 have the same length and the same area when they are arranged opposite each other. The difference is that the thickness of the cathode plate 110 is twice that of the anode plate 111, which is more conducive to electrochemical adsorption. In practical use, the thickness can be set according to the amount of melt, and it is advisable that the thickness of the cathode plate is 2-3 times that of the anode plate.

[0045] Further design could increase the contact area between the cathode and anode plates and the melt, by making the cathode and anode plates mesh-like or claw-like without changing their dimensions. This would be even more effective when combined with a power control mechanism to rotate the cathode and anode plates.

[0046] The cathode plate 110 and the anode plate 111 are arranged opposite to each other and are fixedly connected by a strip-shaped insulating connection part 121. The insulating connection part 121 is provided with a telescopic rod 102, which is connected to a power control mechanism 101. The height of the cathode plate 110 and the anode plate 111 can be adjusted by adjusting the power control mechanism 101.

[0047] As attached Figure 2 As shown, the cathode connection wire 105, the anode connection wire 106, and the insulating connection part 121 are wrapped with heat-insulating material to prevent melting and breakage during use.

[0048] The vacuum melting furnace also includes a furnace body 116 and a furnace cover 108 located on top of the furnace body. A furnace top 103 is formed at the top of the furnace cover 108, and a telescopic rod 102 extends through the furnace top 103, connecting to a power control mechanism 101 outside the melting furnace. A cathode connection line 105 and an anode connection line 106 extend through the furnace top 103, connecting to a purified power supply 109 outside the melting furnace. To ensure the vacuum melting furnace's airtightness and ease of operation, it is more convenient to have the external opening and closing parts located in the same place, and the through-hole parts can be flexibly sealed using sealing materials such as sealing rings.

[0049] The melting device inside the vacuum melting furnace includes a melting crucible 113 and an induction heating coil 112 located outside the melting crucible. The induction heating coil 112 is fixedly connected to a rotating handle 115 located outside the furnace body via a coil connection part 114 that penetrates the furnace body. The rotating handle controls the position of the coil and the crucible, allowing the operator to pour the melted liquid into the molding device from the outside. The lengths of the cathode plate 110 and the anode plate 111 are such that after extending into the bottom of the crucible 113, the insulating connection part 121 remains outside the melting crucible 113.

[0050] The forming device inside the vacuum melting furnace is a copper casting mold 119, which has a sprue 117 and a forming cavity 118. The furnace cover has two observation windows, a first observation window 104 and a second observation window 107, allowing operators to directly observe the internal melting process with the naked eye. These windows can also be used to insert slag removal tools and adjust the melting process as needed. The furnace body 116 also has inlet / outlet ports 120 for vacuuming, passing inert gas, and exhausting gases.

[0051] The method for zirconium-based amorphous melting using the melting apparatus provided in this embodiment is as follows:

[0052] S01, place the zirconium-based amorphous raw material to be melted into the melting crucible 113, close the furnace 108 cover, connect the vacuum device through the inlet / outlet port to evacuate the vacuum, and after the vacuum is completed, fill the furnace with inert argon gas to make the melting furnace atmosphere argon.

[0053] S02, the induction heating coil 112 is turned on for heating and melting. The cathode plate 110 and anode plate 111 in the pre-melting purification mechanism are suspended above the melting crucible 113 and do not contact the melting crucible. The final temperature of the induction coil heating is 220-250℃ higher than the melting point of the raw material to be melted.

[0054] S03. After the zirconium-based amorphous raw material is melted evenly, the slag condition is observed through the observation window. If there is slag, the slag is quickly removed by inserting the slag-removing net through any observation window. Then, the power control mechanism 101 is operated to drive the telescopic rod 102 to send the cathode plate 110 and the anode plate 111 to the bottom of the melting crucible 113.

[0055] S04, turn on the purification power supply 109, set the voltage to 12V, and the time to 1min. The cathode plate 110 and the anode plate 111 adsorb tiny oxide particles.

[0056] The purification time in this step needs to be strictly controlled. If the time is too long, the electrode plate may heat up and melt, and the zirconium-based amorphous melt will also age.

[0057] S05. After purification is complete, operate the power control unit 101 to drive the telescopic rod 102 to lift the cathode plate 110 and anode plate 111 above the melting crucible 113 until no molten liquid drips into the crucible, and then return it to its original position.

[0058] S06, turn off the induction heating coil 112, pour the purified molten liquid into the lower mold 119, and remove it after cooling to obtain the master alloy ingot.

[0059] Appendix Figure 3 The morphology of the zirconium-based amorphous master alloy ingot obtained in the examples is shown under a metallographic microscope (500x). In contrast, [the following text is missing]. Figure 4The image shows the morphology of a zirconium-based amorphous master alloy ingot under a metallographic microscope (500x) before secondary purification treatment. The metallographic tests show that the number of impurities in the zirconium-based amorphous ingot after secondary purification treatment is significantly reduced.

[0060] Both the master alloy ingots that underwent secondary purification and those that did not were molded into strip-shaped specimens with a length of 100 mm, a width of 10 mm, and a thickness of 1 mm. Three-point bending tests were then conducted. The specimens made from the master alloy ingots that underwent secondary purification showed a bending strength of 2000-2700 MPa, while the specimens made from the untreated master alloy ingots only showed a bending strength of 1200-1800 MPa. Comparing the three-point bending strength, the die-cast specimens from the secondary-purified ingots exhibited significantly better strength stability, with a significantly smaller variance than that of the die-cast specimens from the untreated ingots.

[0061] As can be seen from the above embodiments, the oxide impurity content of the zirconium-based amorphous master alloy ingot is significantly reduced after being treated by the smelting method provided in this invention, and the zirconium-based amorphous products made by die casting of the master alloy have more stable performance and better mechanical properties.

[0062] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A zirconium-based amorphous purification and melting device, adapted for use with a vacuum melting furnace, characterized in that, This includes the purification mechanism, the power control mechanism, and the purification power supply. The purification mechanism includes a cathode plate, an anode plate, and a purification power supply. The cathode plate is connected to the purification power supply via a cathode connection line, and the anode plate is connected to the purification power supply via an anode connection line. The cathode plate is a graphite plate, and the anode plate is a high-temperature alloy plate; The cathode plate and the anode plate are arranged opposite to each other and are fixedly connected by an insulating connection part. The insulating connection part is provided with a telescopic rod, which is connected to the power control mechanism. The height of the cathode plate and the anode plate can be adjusted by adjusting the power control mechanism. The vacuum melting furnace includes a furnace body and a furnace cover located on top of the furnace body. The top of the furnace cover is opened into a furnace top. The telescopic rod passes through the furnace top and is connected to the power control mechanism outside the melting furnace. The cathode connection line and the anode connection line pass through the furnace top and are connected to the purification power supply outside the melting furnace. The vacuum melting furnace is equipped with a melting device, which includes a melting crucible and an induction heating coil located outside the melting crucible. The induction heating coil is fixedly connected to a rotating handle located outside the furnace body through a coil connection part that passes through the furnace body. The lengths of the cathode plate and the anode plate are such that, after extending into the bottom of the crucible, the insulating connection portion remains outside the smelting crucible; The vacuum melting furnace is equipped with a forming device, which is a copper casting mold. The copper casting mold is equipped with a sprue and a forming cavity. The furnace cover is provided with two or more observation windows; the furnace body is provided with air inlet and exhaust outlet.

2. A zirconium-based amorphous purification and smelting method, characterized in that, The zirconium-based amorphous purification and melting apparatus as described in claim 1 is used.

3. The zirconium-based amorphous purification and smelting method according to claim 2, characterized in that... It includes the following steps: Place the raw materials to be melted into the melting crucible, close the furnace lid, evacuate the furnace, and fill it with inert gas. The induction heating coil is turned on for heating and melting. The cathode plate and anode plate in the pre-melting purification mechanism are located outside the melting crucible. After the raw materials are melted evenly, the power control mechanism is operated to drive the telescopic rod to send the cathode plate and anode plate to the bottom of the melting crucible. Turn on the purifier power, set the voltage to 6-30V, and the time to 30s-3min; After purification, operate the power control mechanism to drive the telescopic rod to lift the cathode plate and anode plate above the melting crucible until no molten liquid drips into the crucible, and then return them to their original positions; Turn off the induction heating coil, pour the purified molten liquid into the mold below, and remove it after cooling.

4. The zirconium-based amorphous purification and smelting method according to claim 3, characterized in that, During the heating and melting process, the final temperature of the induction coil is 220-250°C higher than the melting point of the raw material to be melted.

5. The zirconium-based amorphous purification and smelting method according to claim 4, characterized in that, The cathode plate and the anode plate have the same length and are arranged opposite each other with the same area; the thickness of the cathode plate is 2-3 times that of the anode plate.

6. The zirconium-based amorphous purification and smelting method according to claim 5, characterized in that, The cathode plate and the anode plate are configured as mesh or claw-shaped.

7. The zirconium-based amorphous purification and smelting method according to claim 6, characterized in that, The cathode connection wire, the anode connection wire, and the insulating connection portion are wrapped with heat-insulating material.

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