Intermediate alloy containing zirconium and magnesium, as well as its manufacturing method and use

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 performance and are widely used in various fields. In research, it has been 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 nuclei 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 15 - 40% CaCl2, 13 - 25% BaCl2, 0 - 10% NaCl, 1 - 10% CaF2, 0 - 6% Ti / Zr powder, 0 - 10% K2TiF6 / K2ZrF6, and the balance 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. In a mixed gas composed of CO2 and SF6, zirconium chloride is gradually added to molten metallic magnesium to obtain a magnesium-zirconium intermediate alloy. This method solves the problem of non-uniform distribution of zirconium in the magnesium-zirconium intermediate alloy. Since the particle size of zirconium particles in the obtained magnesium-zirconium intermediate alloy is large, when added to molten magnesium as an intermediate 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 aims to provide a method for producing an intermediate alloy containing zirconium and magnesium. This method can effectively reduce the particle size of zirconium particles in the intermediate alloy. Furthermore, this method can reduce the salt content in the intermediate alloy.

[0006] Furthermore, the present invention aims to provide an intermediate alloy containing zirconium and magnesium.

[0007] Furthermore, the present invention aims to provide the use of an intermediate alloy containing zirconium and magnesium.

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

[0009] In one embodiment, the present invention is The process includes the steps of forming magnesium and metallic RE in a rare-earth-magnesium alloy solution in the presence of a protective gas, and reacting chloride particles with the rare-earth-magnesium alloy solution in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium. The chloride particles are, Zirconium chloride 20-80 wt%, Potassium chloride 10-40 wt%, and It contains an ingredient of 10-40 wt% sodium chloride. The present invention provides a method for producing an intermediate alloy containing zirconium and magnesium, wherein the metal RE is one or more selected from lanthanum, cerium, praseodymium, or neodymium.

[0010] According to the manufacturing method of the present invention, the chloride particles are preferably obtained by melting, pouring, and grinding a mixture containing zirconium chloride, potassium chloride, and sodium chloride.

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

[0012] According to the manufacturing method of the present invention, the protective gas preferably contains an inert gas and SF6 in a volume ratio of (15-25):1.

[0013] According to the manufacturing method of the present invention, it is preferable that the amount of magnesium used is 50 to 150 parts by weight, the amount of metal RE used is 14 to 35 parts by weight, and the amount of chloride particles used is 75 to 250 parts by weight.

[0014] According to the manufacturing method of the present invention, metal RE is added to molten magnesium while stirring, and after the metal RE has been completely added to the molten magnesium, stirring is continued for 10 to 120 minutes to obtain a rare earth-magnesium alloy solution, and the rotation speed of the stirring device used to stir the molten magnesium is preferably 100 to 300 r / min.

[0015] According to the manufacturing method of the present invention, chloride particles are added to a rare earth-magnesium alloy solution while being stirred and reacted for 30 to 150 minutes, and the rotation speed of the stirring equipment used to stir the rare earth-magnesium alloy solution is preferably 100 to 300 r / min.

[0016] The manufacturing method according to the present invention preferably further includes a step of refining the reaction product obtained by reacting chloride particles with a rare earth-magnesium alloy solution using an inert gas.

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

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

[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 magnesium alloy manufacturing process, the settling rate of zirconium particles in molten magnesium is slowed, and the utilization rate of zirconium can be improved. [Modes for carrying out the invention]

[0020] The present invention will be further described below with reference to specific examples, but the scope of the present invention is not limited to these.

[0021] <Method for producing an intermediate alloy containing zirconium and magnesium> The intermediate alloy according to the present invention contains zirconium and magnesium. The method for producing the intermediate alloy according to the present invention includes the steps of forming magnesium and metallic RE in a rare earth-magnesium alloy solution in the presence of a protective gas, and reacting chloride particles with the rare earth-magnesium alloy solution in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium. A detailed explanation follows below.

[0022] The protective gas according to the present invention comprises an inert gas and SF6. In some embodiments, the protective gas consists of an inert gas and SF6. 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] The volume ratio of the inert gas to SF6 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 under 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 to 40 ml / min, preferably 10 to 30 ml / min, and more preferably 15 to 20 ml / min.

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

[0026] Magnesium may be used in the form of molten magnesium. The temperature of the molten magnesium may be 650 to 830 °C, preferably 700 to 800 °C, and more preferably 740 to 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 to 2.5):1, preferably (1 to 2):1, and more preferably (1.25 to 1.75):1.

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

[0029] In some embodiments, a rare earth-magnesium alloy solution is obtained by adding a metallic RE to molten magnesium. Preferably, the metallic RE is added to the molten magnesium while stirring. The rotational speed of the stirring device for stirring the molten magnesium may be 100 to 300 r / min, preferably 150 to 200 r / min. According to one embodiment of the present invention, after the metallic RE has been completely added to the molten magnesium, stirring is continued for 10 to 120 mins to obtain a rare earth-magnesium alloy solution. Preferably, the stirring is continued for 20 to 100 mins, and more preferably for 30 to 60 mins.

[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. This makes it possible to reduce the particle size of the zirconium particles in the intermediate alloy.

[0031] In the chloride particles according to the present invention, the zirconium chloride content 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 potassium chloride content 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 sodium chloride content is 10 to 40 wt%, preferably 20 to 30 wt%, and more preferably 18 to 26 wt%.

[0034] By adjusting the content of zirconium chloride, potassium chloride, and sodium chloride within the above ranges, the particle size of zirconium particles in the intermediate 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 irregularly shaped. The particle size of the chloride particles may be 0.1 to 0.5 mm, preferably 0.15 to 0.4 mm, and more preferably 0.15 to 0.3 mm. This makes it possible to reduce the particle size of zirconium particles in the intermediate alloy.

[0036] The chloride particles according to the present invention can be obtained by melting, pouring, and grinding a mixture containing zirconium chloride, potassium chloride, and sodium chloride. Preferably, the mixture consists of zirconium chloride, potassium chloride, and sodium chloride. This makes it possible to reduce the particle size of the zirconium particles in the intermediate alloy.

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

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

[0039] The rotational speed of the stirring device for stirring the rare earth-magnesium alloy solution may be 100 to 300 r / min, preferably 120 to 260 r / min, and more preferably 150 to 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 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 one embodiment of the present invention, the inert gas is argon.

[0041] Specifically, the reaction product is refined by blowing in an inert gas, and then suspended impurities on the surface of the reaction product are removed to obtain an intermediate alloy solution. The intermediate alloy solution is then 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 minutes, preferably 10 to 40 minutes, and more preferably 20 to 30 minutes.

[0044] <Intermediate alloy containing zirconium and magnesium> The intermediate alloy containing zirconium and magnesium according to the present invention is obtained by the manufacturing method described above. The average particle size of the 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 the 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 110 ppm or less, and more preferably 100 ppm or less. In some embodiments, the chloride ion content is 85 to 110 ppm.

[0046] <Use of intermediate alloys 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 1-3 A mixture consisting of zirconium chloride, potassium chloride, and sodium chloride is provided. The mixture was melted to obtain a molten mixture. After pouring the molten mixture, it was pulverized to obtain chloride particles with a particle size of 0.15 mm.

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

[0049] TIFF0007902283000001.tif56170

[0050] Examples 1-4 A protective gas containing argon and SF6 in a volume ratio of 19:1 is introduced into the melting furnace, which serves as the reaction apparatus, at a flow rate of 15 ml / min.

[0051] Metal RE was added to molten magnesium while stirring, and the stirring device used to stir the molten magnesium was set to a rotation speed of 150 r / min. After the metal RE was completely added to the molten magnesium, the molten magnesium was continued to stir for t1 hours to obtain a rare earth-magnesium alloy solution.

[0052] Chloride particles were added to a stirred rare-earth-magnesium alloy solution and reacted to obtain a reaction product.

[0053] The reaction product was refined by blowing argon into it, and then suspended impurities on the surface of the reaction product were removed to obtain an intermediate alloy solution. The intermediate alloy solution was poured to obtain the intermediate alloy.

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

[0055] Polished surface-finished alloy samples were observed and analyzed using a high-resolution field emission scanning electron microscope (EDS). Zirconium particle size was measured using EDS energy spectroscopy and the electron microscope's dimensional measurement function. Statistical analysis of zirconium particle size within the scanning electron microscope image area was performed in combination with ImagePro software to obtain average particle size data.

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

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

[0058] TIFF0007902283000002.tif183170

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

[0060] The present invention is not limited to the embodiments described above, and any modifications, improvements, substitutions, etc., that a person skilled in the art could conceive of, without departing from the spirit of the invention, are included within the scope of the present invention.

Claims

1. The process includes the steps of forming magnesium and metallic RE in a rare-earth-magnesium alloy solution in the presence of a protective gas, and reacting chloride particles with the rare-earth-magnesium alloy solution in the presence of a protective gas to obtain an intermediate alloy containing zirconium and magnesium. The chloride particles are, Zirconium chloride 20-80 wt%, Potassium chloride 10-40 wt%, and It consists of 10-40 wt% sodium chloride. A method for producing an intermediate alloy containing zirconium and magnesium, characterized in that the metal RE is one or more selected from lanthanum, cerium, praseodymium, or neodymium.

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

3. The manufacturing method according to claim 1, characterized in that the particle size of the chloride particles is 0.1 to 0.5 mm.

4. The protective gas is an inert gas and SF ６ The manufacturing method according to claim 1, characterized in that it contains the two in a volume ratio of (15 to 25):

1.

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

6. In a manufacturing method for obtaining a rare earth-magnesium alloy solution, in which a metallic RE is added to molten magnesium while stirring, and after the metallic RE has been completely added to the molten magnesium, stirring is continued for 10 to 120 minutes, The manufacturing method according to claim 1, characterized in that the rotation speed of the stirring equipment for stirring the molten magnesium is 100 to 300 r / min.

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

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

Images