Master alloy containing zirconium and magnesium, and method for producing and using the same

Abstract

The present invention discloses an intermediate alloy containing zirconium and magnesium, and a method for producing and using the same. The production method includes a step of forming magnesium and metal RE into a rare earth-magnesium alloy liquid in the presence of a protective gas, and a step of reacting chloride particles with the rare earth-magnesium alloy liquid in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium. This production method can effectively reduce the particle size of zirconium particles in the intermediate alloy.

Description

Technical Field

[0001] The present invention relates to an intermediate alloy containing zirconium and magnesium, and a method for producing and using the same.

Background Art

[0002] Magnesium alloys have excellent properties and are widely used in various fields. Research has found that by adding zirconium to magnesium alloys, the crystal grains of magnesium alloys can be refined. During the crystallization process of magnesium alloys, zirconium particles precipitate preferentially. Since zirconium particles have the same hexagonal close-packed structure and similar lattice constants as magnesium, they can serve as nuclei for heterogeneous nucleation during alloy crystallization, effectively refining the casting structure of the alloy and improving the uniformity of the structure and the stability of performance.

[0003] CN114182130A discloses a refining agent for magnesium alloys. This refining agent contains components in a mass ratio of CaCl 2 15 - 40%, BaCl 2 13 - 25%, NaCl 0 - 10%, CaF 2 1 - 10%, Ti / Zr powder 0 - 6%, K 2 TiF 6 / K 2 ZrF 6 0 - 10%, and the balance of KCl. This composition contains a large amount of salt components and does not form an intermediate alloy when used as a refining agent.

[0004] CN108048718A discloses a method for producing a magnesium-zirconium intermediate alloy. CO 2 and SF 6In a mixed gas consisting of, zirconium chloride is gradually added to molten metallic magnesium to obtain a magnesium-zirconium master alloy. This method solves the problem of non-uniform distribution of zirconium in the magnesium-zirconium master alloy. Since the particle size of zirconium particles in the obtained magnesium-zirconium master alloy is large, when the master alloy is added to molten magnesium as a master alloy, the zirconium particles settle to the bottom of the molten magnesium, which is disadvantageous for improving the utilization rate of zirconium.

Summary of the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a master alloy containing zirconium and magnesium. This production method can effectively reduce the particle size of zirconium particles in the master alloy. Furthermore, this method can reduce the salt content in the master alloy.

[0006] Another object of the present invention is to provide a master alloy containing zirconium and magnesium.

[0007] Furthermore, an object of the present invention is to provide the use of a master alloy containing zirconium and magnesium.

[0008] The above object is achieved by the following configuration.

[0009] In one aspect, the present invention forming magnesium and metallic RE into a rare earth-magnesium alloy liquid in the presence of a protective gas; and reacting chloride particles with the rare earth-magnesium alloy liquid in the presence of a protective gas to obtain a master alloy containing zirconium and magnesium, wherein the chloride particles contain 20 to 80 wt% of zirconium chloride, 10 to 40 wt% of potassium chloride, and 10 to 40 wt% of sodium chloride, Provided is a method for producing an intermediate alloy containing zirconium and magnesium, wherein the rare earth metal RE is one or more selected from lanthanum, cerium, praseodymium, or neodymium.

[0010] According to the production method of the present invention, it is preferable that the chloride particles are obtained by melting, casting, and pulverizing a mixture containing zirconium chloride, potassium chloride, and sodium chloride.

[0011] According to the production method of the present invention, the particle size of the chloride particles is preferably 0.1 to 0.5 mm.

[0012] According to the production method of the present invention, the protective gas preferably contains an inert gas and SF 6 in a volume ratio of (15 to 25):1.

[0013] According to the production method of the present invention, the amount of magnesium used is preferably 50 to 150 parts by weight, the amount of rare earth metal RE used is preferably 14 to 35 parts by weight, and the amount of chloride particles used is preferably 75 to 250 parts by weight.

[0014] According to the production method of the present invention, the rare earth metal RE is added to the molten magnesium during stirring. After the rare earth metal RE is completely added to the molten magnesium, stirring is continued for 10 to 120 minutes to obtain a rare earth-magnesium alloy liquid. The rotation speed of the stirring device for stirring the molten magnesium is preferably 100 to 300 r / min.

[0015] According to the production method of the present invention, the chloride particles are added to the rare earth-magnesium alloy liquid during stirring and reacted for 30 to 150 minutes. The rotation speed of the stirring equipment for stirring the rare earth-magnesium alloy liquid is preferably 100 to 300 r / min.

[0016] According to the production method of the present invention, it is preferable to further include a step of refining the reaction product obtained by reacting the chloride particles with the rare earth-magnesium alloy liquid using an inert gas.

[0017] In another aspect, the present invention provides an intermediate alloy containing zirconium and magnesium obtained by the above manufacturing method.

[0018] In yet another aspect, the present invention provides the use of the intermediate alloy containing zirconium and magnesium in the production of magnesium alloys.

[0019] The manufacturing method according to the present invention can reduce the particle size of zirconium particles in the intermediate alloy. When the intermediate alloy according to the present invention is applied to the manufacturing process of magnesium alloys, the sedimentation rate of zirconium particles in the molten magnesium is slowed down, and the utilization rate of zirconium can be improved.

Embodiments for Carrying Out the Invention

[0020] Hereinafter, the present invention will be further described with specific examples, but the scope of the present invention is not limited thereto.

[0021] <Manufacturing Method of Intermediate Alloy Containing Zirconium and Magnesium> The intermediate alloy according to the present invention contains zirconium and magnesium. The manufacturing method of the intermediate alloy according to the present invention includes a step of forming magnesium and metal RE into a rare earth-magnesium alloy liquid in the presence of a protective gas, and a step of reacting chloride particles with the rare earth-magnesium alloy liquid in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium. Hereinafter, it will be described in detail.

[0022] The protective gas according to the present invention includes an inert gas and SF 6 and. In some embodiments, the protective gas consists of an inert gas and SF 6 The inert gas is one or more selected from helium, neon, argon, krypton, and xenon. Preferably, the inert gas is one or more selected from helium, neon, or argon. More preferably, the inert gas is argon gas.

[0023] Inert gas and SF 6 The volume ratio of to may be (15 - 25):1, preferably (17 - 22):1, and more preferably (19 - 20):1.

[0024] According to an embodiment of the present invention, by introducing a protective gas into the reaction device, the reaction system is reacted in a protective gas atmosphere. The reaction device may be a melting furnace. The flow rate of the protective gas introduced into the reaction device may be 5 - 40 ml / min, preferably 10 - 30 ml / min, and more preferably 15 - 20 ml / min.

[0025] The usage amount of magnesium may be 50 - 150 parts by weight, preferably 70 - 130 parts by weight, and more preferably 75 - 105 parts by weight.

[0026] Magnesium may be used in the form of molten magnesium. The temperature of the molten magnesium may be 650 - 830 °C, preferably 700 - 800 °C, and more preferably 740 - 780 °C. Thereby, while sufficiently reacting the molten magnesium and the metal RE, the volatilization of the raw materials can be reduced, and the yield and safety can be improved.

[0027] The metal RE is one or more selected from lanthanum, cerium, praseodymium, or neodymium. The metal RE may be a single metal or an alloy. In some embodiments, the metal RE is one selected from lanthanum, cerium, or neodymium. In another embodiment, the metal RE is a lanthanum - cerium alloy. The mass ratio of the lanthanum element to the cerium element in the lanthanum - cerium alloy may be (0.5 - 2.5):1, preferably (1 - 2):1, and more preferably (1.25 - 1.75):1.

[0028] The usage amount of the metal RE may be 14 - 35 parts by weight, preferably 16 - 30 parts by weight, and more preferably 20 - 27 parts by weight.

[0029] In some embodiments, a rare earth metal RE is added to a molten magnesium metal to obtain a rare earth-magnesium alloy liquid. Preferably, the rare earth metal RE is added to the molten magnesium metal during stirring. The rotation speed of the stirring device for stirring the molten magnesium metal may be 100 to 300 r / min, preferably 150 to 200 r / min. According to an embodiment of the present invention, after the rare earth metal RE is completely added to the molten magnesium metal, stirring is continued for 10 to 120 minutes to obtain a rare earth-magnesium alloy liquid. Preferably, the time for continuing stirring is 20 to 100 minutes, and more preferably, the time for continuing stirring is 30 to 60 minutes.

[0030] The chloride particles according to the present invention contain zirconium chloride, potassium chloride, and sodium chloride. In some embodiments, the chloride particles consist of zirconium chloride, potassium chloride, and sodium chloride. Thereby, the particle size of the zirconium particles in the master alloy can be reduced.

[0031] In the chloride particles according to the present invention, the content of zirconium chloride is 20 to 80 wt%, preferably 30 to 70 wt%, and more preferably 35 to 60 wt%.

[0032] In the chloride particles according to the present invention, the content of potassium chloride is 10 to 40 wt%, preferably 20 to 30 wt%, and more preferably 18 to 26 wt%.

[0033] In the chloride particles according to the present invention, the content of sodium chloride is 10 to 40 wt%, preferably 20 to 30 wt%, and more preferably 18 to 26 wt%.

[0034] By setting the contents of zirconium chloride, potassium chloride, and sodium chloride within the above ranges, the particle size of the zirconium particles in the master alloy can be reduced.

[0035] The present invention has no restrictions on the shape of the chloride particles. The chloride particles may be circular, triangular, rectangular, cylindrical or irregular in shape. The particle size of the chloride particles may be 0.1 - 0.5 mm, preferably 0.15 - 0.4 mm, more preferably 0.15 - 0.3 mm. Thereby, the particle size of the zirconium particles in the master alloy can be reduced.

[0036] The chloride particles according to the present invention can be obtained by melting, casting and pulverizing a mixture containing zirconium chloride, potassium chloride and sodium chloride. Preferably, the mixture consists of zirconium chloride, potassium chloride and sodium chloride. Thereby, the particle size of the zirconium particles in the master alloy can be reduced.

[0037] In the present invention, the amount of the chloride particles used may be 75 - 250 parts by weight, preferably 85 - 220 parts by weight, more preferably 100 - 160 parts by weight, and most preferably 100 - 140 parts by weight.

[0038] In some embodiments, the chloride particles are added to the rare earth - magnesium alloy liquid for reaction. Preferably, the chloride particles are added to the stirring rare earth - magnesium alloy liquid for reaction. In this process, the rare earth elements in the rare earth - magnesium alloy liquid and zirconium chloride undergo a reduction reaction to form zirconium and rare earth chlorides. The reaction time may be 30 - 150 min, preferably 40 - 120 min, more preferably 50 - 100 min.

[0039] The rotation speed of the stirring device for stirring the rare earth - magnesium alloy liquid may be 100 - 300 r / min, preferably 120 - 260 r / min, more preferably 150 - 220 r / min.

[0040] In some embodiments, the method of the present invention further includes a step of refining a reaction product obtained by reacting chloride particles with a liquid of a rare earth-magnesium alloy using an inert gas. The inert gas is one or more selected from helium, neon, argon, krypton, and xenon. Preferably, the inert gas is one or more selected from helium, neon, or argon. According to an embodiment of the present invention, the inert gas is argon.

[0041] Specifically, an inert gas is blown into the reaction product for refining, and then, floating impurities on the surface of the reaction product are removed to obtain an intermediate alloy liquid. The intermediate alloy liquid is poured to obtain an intermediate alloy containing zirconium and magnesium.

[0042] The flow rate of the inert gas may be 2 to 40 ml / min, preferably 5 to 30 ml / min, and more preferably 10 to 20 ml / min.

[0043] The refining time may be 5 to 60 min, preferably 10 to 40 min, and more preferably 20 to 30 min.

[0044] <Intermediate alloy containing zirconium and magnesium> The intermediate alloy containing zirconium and magnesium according to the present invention is obtained by the above manufacturing method. The average particle size of zirconium particles in the intermediate alloy containing zirconium and magnesium is 900 nm or less, preferably 800 nm or less, and more preferably 600 nm or less. In some embodiments, the average particle size of zirconium particles is 550 to 600 nm.

[0045] In the intermediate alloy containing zirconium and magnesium, the chloride ion content is 150 ppm or less, preferably the chloride ion content is 110 ppm or less, and more preferably the chloride ion content is 100 ppm or less. In some embodiments, the chloride ion content is 85 to 110 ppm.

[0046] <Use of an intermediate alloy containing zirconium and magnesium> The intermediate alloy containing zirconium and magnesium according to the present invention can be used as an intermediate alloy in the magnesium alloy manufacturing process and can play a role in refining the crystal grains of the magnesium alloy. Therefore, the present invention provides the use of the intermediate alloy containing zirconium and magnesium in the manufacture of magnesium alloys. Preferably, the intermediate alloy containing zirconium and magnesium according to the present invention is used as a crystal grain refiner for magnesium alloys.

[0047] Preparation Examples 1 to 3 A mixture consisting of zirconium chloride, potassium chloride, and sodium chloride is provided. The mixture is melted to obtain a molten mixture. After pouring the molten mixture, it is pulverized to obtain chloride particles with a particle size of 0.15 mm.

[0048] The contents of zirconium chloride, potassium chloride, and sodium chloride in the mixture are as shown in Table 1.

[0049] TIFF2025516382000001.tif56170

[0050] Examples 1 to 4 Argon and SF 6 A protective gas containing argon and SF in a volume ratio of 19:1 is introduced into the melting furnace as a reactor at a flow rate of 15 ml / min.

[0051] Metal RE is added to the molten magnesium while stirring, and the rotation speed of the stirring device for stirring the molten magnesium is 150 r / min. After the metal RE is completely added to the molten magnesium, the molten magnesium is stirred for t 1 hours and a rare earth-magnesium alloy liquid is obtained.

[0052] The chloride particles are added to the stirring rare earth-magnesium alloy liquid to react to obtain a reaction product.

[0053] Argon was blown into the reaction product for refining, and then the floating impurities on the surface of the reaction product were removed to obtain an intermediate alloy liquid. The intermediate alloy liquid was poured to obtain an intermediate alloy.

[0054] The average particle size of zirconium particles in the intermediate alloy was measured, and the specific method is as follows.

[0055] The polished surface-finished alloy sample was observed and regionally analyzed using a high-resolution field emission scanning electron microscope. The particle size of zirconium particles was measured by the EDS energy spectrum and the dimension measurement function of the electron microscope. In combination with the software ImagePro, statistical analysis of the particle size of zirconium particles in the image region of the scanning electron microscope was performed to obtain the average particle size data.

[0056] The chlorine ion content in the intermediate alloy was measured using glow discharge mass spectrometry (GDMS).

[0057] The specific parameters are as shown in Table 2. The average particle size of zirconium particles and the chlorine ion content are as shown in Table 2.

[0058] TIFF2025516382000002.tif183170

[0059] Note: In the lanthanum-cerium alloy, the mass ratio of lanthanum element to cerium element is 0.75:0.5.

[0060] The present invention is not limited to the above embodiments, and any deformation, improvement, substitution, etc. that can be conceived by those skilled in the art without departing from the spirit of the present invention shall be included in the scope of the present invention.

Claims

1. forming magnesium and metallic RE into a rare earth-magnesium alloy liquid in the presence of a protective gas; and reacting chloride particles with the rare earth-magnesium alloy liquid in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium; The chloride particles are Zirconium chloride 20-80wt%, Potassium chloride 10-40 wt%; and It contains 10-40wt% sodium chloride.

11. A method for producing an intermediate alloy containing zirconium and magnesium, wherein the metal RE is one or more selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium.

2. 2. The method according to claim 1, wherein the chloride particles are obtained by melting, pouring and grinding a mixture containing zirconium chloride, potassium chloride and sodium chloride.

3. 3. The method according to claim 1, wherein the chloride particles have a particle size of 0.1 to 0.5 mm.

4. The protective gas is an inert gas and SF 6 and in a volume ratio of (15-25):

1.

5. The method according to claim 1, characterized in that the amount of magnesium used is 50-150 parts by weight, the amount of metal RE used is 14-35 parts by weight, and the amount of chloride particles used is 75-250 parts by weight.

6. A method for producing a rare earth-magnesium alloy liquid, comprising: adding a metallic RE to molten magnesium during stirring; and continuing stirring for 10 to 120 min after the metallic RE has been completely added to the molten magnesium, The manufacturing method according to claim 1, characterized in that the rotation speed of the stirring device for stirring the molten magnesium is 100 to 300 r / min.

7. The manufacturing method according to claim 1, characterized in that, in the manufacturing method in which chloride particles are added to a stirred rare earth-magnesium alloy liquid and reacted for 30 to 150 min, the rotation speed of the stirring equipment for stirring the rare earth-magnesium alloy liquid is 100 to 300 r / min.

8. 2. The method according to claim 1, further comprising the step of refining a reaction product obtained by reacting the chloride particles with the rare earth-magnesium alloy liquid using an inert gas.

9. An intermediate alloy containing zirconium and magnesium, characterized in that the intermediate alloy is obtained by the manufacturing method according to any one of claims 1 to 8.

10. 10. Use of the zirconium and magnesium containing intermediate alloy according to claim 9 in the production of magnesium alloys.

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