WO2014207834A1 - Al-Sc合金の製造方法 - Google Patents
Al-Sc合金の製造方法 Download PDFInfo
- Publication number
- WO2014207834A1 WO2014207834A1 PCT/JP2013/067503 JP2013067503W WO2014207834A1 WO 2014207834 A1 WO2014207834 A1 WO 2014207834A1 JP 2013067503 W JP2013067503 W JP 2013067503W WO 2014207834 A1 WO2014207834 A1 WO 2014207834A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- molten
- reaction
- metal
- molten salt
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/06—Obtaining aluminium refining
- C22B21/062—Obtaining aluminium refining using salt or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
Definitions
- the present invention relates to an Al—Sc alloy production method suitable for producing an Al—Sc alloy, and an Al—Sc alloy obtained by the production method.
- Patent Document 1 discloses that by including 0.05 to 0.3% by mass of Sc and 0.1 to 0.4% by mass of Zr in a pure Al matrix, electrical conductivity is good and mechanical properties are improved. It has been introduced that an aluminum alloy material having high strength and excellent heat resistance can be obtained as an aluminum-based alloy wiring material.
- an aluminum-based alloy containing Sc is expected to be industrially useful, conventionally, its use has been extremely limited. This is because the metal Sc is easily oxidized and the reduction in obtaining the metal Sc from a scandium compound (Sc compound) such as a halide or a chalcogenide of Sc is accompanied by difficulty. That is, in order to obtain Sc as a metal, an alkali metal such as Na, which is more easily oxidized than Sc, or an alkaline earth metal such as Ca or Mg is used as a reducing agent, and the Sc compound is reduced or melted under heating. This is because it is necessary to reduce by salt electrolysis.
- Sc compound scandium compound
- Ca or Mg alkaline earth metal
- Patent Document 2 Sc halide is charged into a vacuum reaction vessel together with metal Ca, metal Zn, etc., and the Sc halide is reduced with metal Ca to obtain a Sc—Zn alloy.
- the Sc—Zn alloy phase is separated from the halide phase containing Ca oxide and pulverized, and the alloy powder obtained by pulverization is oxidized to form a thin oxide film on the powder surface.
- a technique is disclosed in which a metal Sc powder is obtained by charging the inside of a vacuum vessel having an inert gas atmosphere and heating it under vacuum to volatilize and evaporate Zn or the like as an alloy component.
- a molten metal Al floated in an upper layer in a molten salt electrolytic bath mainly composed of an alkali metal or alkaline earth metal fluoride and a fluoride of a rare earth element such as Sc, Y, or a lanthanoid.
- a cathode Is used as a cathode, and the anode is protected with an insulator so as not to come into contact with the molten metal Al in the upper layer, and an electrolytic reduction is performed to manufacture an aluminum-based alloy containing a rare earth element.
- aluminum containing Sc is allowed to react with the metal Al as it is without using a step of reducing Sc from the compound to a metal.
- Several techniques for obtaining a base alloy have been proposed.
- Patent Document 4 discloses a technique in which a rare earth element compound is reacted with aluminum in the presence of a calcium chloride flux to obtain an aluminum-based alloy containing the rare earth element.
- a halogenated Sc such as ScF 3 and a metal Al are charged into a reaction vessel together with a metal Ca serving as a reducing agent, LiF serving as a flux, and CaCl 2.
- a metal Ca serving as a reducing agent
- LiF serving as a flux
- CaCl 2 serving as a flux
- the solidification temperature of Al or 100 ° C. lower than the solidification temperature By cooling the range up to the temperature at a cooling rate of 10 to 70 ° C. per minute, Sc high density precipitates and low density precipitates are formed in the Al—Sc alloy.
- rare earth element oxide or halide powder such as Sc is mixed with powder of light metal such as Al, Mg, etc., and the resulting mixture is formed into a pellet by compression molding, and then the surface of the pellet Disclosure of a technology for obtaining a light metal alloy containing a rare earth element by increasing the wettability of the light metal in the molten metal and then putting it into a molten light metal bath and reducing the rare earth oxide or halide with the light metal Has been.
- Patent Document 7 discloses a technique for reacting an oxide of a rare earth element with a metal Al as a method for producing an aluminum-based alloy containing Y and a lanthanoid rare earth element.
- Patent Document 4 a rare earth element compound as a raw material is reduced with metal Al, and the reaction temperature at that time is required to be 1200 ° C. or higher.
- AlCl 3 , HCl, etc. which are reaction products and have a high vapor pressure, volatilize, and such gas is very corrosive, and it is necessary to use an expensive corrosion-resistant material as a crucible material.
- there are limitations in handling such as environmental pollution countermeasures and there is a problem that the oxidation consumption of Al and the required heat energy are enormous, which is not economical.
- Patent Document 5 since the halogenated Sc is reduced under an inert gas atmosphere with a metal Ca serving as a reducing agent, the residual portion of the metal Ca is evaporated and removed under a vacuum atmosphere.
- metal Ca serving as a reducing agent
- Patent Document 6 a rare earth element oxide or halide powder such as Sc is mixed with a light metal powder and then formed into a pellet by compression molding. Further, the pellet surface is wetted with respect to the melt of the light metal. As in the case of Patent Document 5, it is difficult to reduce costs and improve economy, because the manufacturing process is multi-stage, such as the need to improve performance.
- the rare earth element is Y and lanthanoid and Sc is not contained, but the melt of the aluminum-based alloy containing the rare earth element produced in the reaction process is the other reaction product. It is located above the aluminum oxide powder that is exposed to the outside atmosphere, so the reaction system must be maintained in an inert gas atmosphere, and the raw material is heated and melted in an inert gas atmosphere. Therefore, even in the technique of Patent Document 7, there is a problem that it is difficult to reduce cost and improve economy.
- the present invention has been devised in view of such a viewpoint, and is a method suitable for manufacturing an Al—Sc alloy, including equipment for heating in an inert gas atmosphere or a vacuum atmosphere.
- reducing agents such as metal Ca and equipment and power for molten salt electrolysis are not required, and heating up to 1050 ° C. is sufficient, and the manufacturing process is simple and simple.
- An object of the present invention is to provide a method for producing an Al—Sc alloy that can reduce the risk of occurrence and can be continuously operated, and can easily improve the economy.
- the present invention relates to metal aluminum (Al), one or more metal fluoride salts selected from the group consisting of alkali metal fluorides, alkaline earth metal fluorides and aluminum fluorides, scandium ( (Sc) oxide and / or a scandium compound comprising a fluoride salt is charged into a reaction vessel, and the reaction system comprises the metal aluminum (Al), the metal fluoride salt and the scandium compound in the reaction vessel.
- reaction temperature of the reaction system is in the range of 700 to 1050 ° C., and the metal fluoride salt has a melting point lower than the reaction temperature and a density of molten metal aluminum at the reaction temperature of the reaction system.
- a metal fluoride salt having a density in the range of 70 to 95% is used, and in the reaction system in the reaction vessel, the molten salt layer is an upper layer and the molten metal layer is a lower layer. This is a method for producing an Al—Sc alloy.
- the present invention is an Al—Sc alloy manufactured by the above-described method.
- the metal fluoride salt charged into the reaction vessel to form the molten salt layer is selected from the group consisting of alkali metal fluorides, alkaline earth metal fluorides, and aluminum fluoride (AlF 3 ).
- the alkali metal fluorides include lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), etc.
- Examples of alkaline earth metal fluorides include beryllium fluoride (BeF 2 ), magnesium fluoride (MgF 2 ), and calcium fluoride (CaF 2 ).
- the reaction temperature of the reaction system in the range of 700 to 1050 ° C.
- the desired density at the reaction temperature in the range of 70 to 95% of the density of the molten metal Al at the reaction temperature of the reaction system.
- it is a mixture of LiF and NaF. More preferably, the mixture of LiF and NaF is in a mass ratio (LiF: NaF) in the range of 7: 5 to 8: 5.
- Metal fluoride salt comprising such mixtures, an a melting point 652 ⁇ 675 ° C., a 1.99kg / dm 3 when its density is 760 °C, 1.88kg / dm 3 when 980 ° C. In the molten state, it is not compatible with the molten metal Al or the molten Al—Sc alloy forming the molten metal layer.
- the scandium compound (Sc compound) that is charged into the molten salt layer and generates scandium ions (Sc 3+ ) during the reaction is an oxide (Sc 2 O 3 ) and / or fluoride salt of scandium (Sc).
- a (ScF 3) according to the production of a continuous Al-Sc based alloys aspect, preferably scandium oxide (Sc 2 O 3).
- the reaction system in the reaction vessel it is necessary that the molten salt layer is an upper layer and the molten metal layer is a lower layer, and the molten metal layer is not in contact with air, and the reaction system is left standing.
- the reaction may be allowed to proceed, and as long as the molten metal layer does not come into contact with air, the reaction system may be stirred as necessary, thereby further promoting the chemical reaction.
- the reaction temperature of this reaction system is usually in the range of 700 ° C. or higher and 1050 ° C. or lower, and when it is lower than 700 ° C., it approaches the melting point of Al (660 ° C.), and Al 3 Sc is locally generated and reacted.
- the product Al-Sc alloy may become inhomogeneous, and when using scandium (Sc) oxide (Sc 2 O 3 ) as a scandium compound (Sc compound) Since the solubility of scandium oxide (Sc 2 O 3 ) is low, there is a problem that the chemical reaction rate is limited. On the other hand, when the temperature is higher than 1050 ° C., the required heat energy becomes large and expensive heat-resistant material. Must be used as a reaction vessel, and the vapor pressure of the molten salt becomes high, resulting in a large evaporation loss. This increases the cost and causes problems such as environmental pollution countermeasures. .
- the density of the molten salt at the reaction temperature of the reaction system is the reaction of the reaction system. It should be in the range of 70% or more and 95% or less of the density of molten metal aluminum at a temperature, and in order to make it less than 70%, the blending ratio of expensive lithium fluoride (mp: 848 ° C) having a high melting point is required. On the other hand, there is a problem that the economy is lowered because it is necessary to increase the density.
- the density of the molten salt increases with the dissolution of the Sc compound, and the density of the molten salt layer is reduced.
- the molten metal layer is exposed on the upper part of the molten salt layer and comes into contact with air, and the molten metal reacts with oxygen in the air to oxidize, thereby reducing the recovery rate of the Al—Sc alloy for manufacturing purposes. The problem arises.
- metal aluminum (Al), metal fluoride salt and Sc compound are placed in the reaction vessel. Then, the reaction system may be formed by raising the temperature to the reaction temperature, but the metal aluminum (Al) and the metal fluoride salt are charged into the reaction vessel and the temperature is raised to the reaction temperature in advance. A molten metal layer and a molten salt layer may be formed, and then an Sc compound may be added into the molten salt layer to generate scandium ions (Sc 3+ ) in the molten salt layer.
- equipment for heating under an inert gas atmosphere or vacuum atmosphere equipment for reducing agent such as metal Ca, molten salt electrolysis, and power
- heating up to 1050 ° C is sufficient, the manufacturing process is simple and simple, there is little risk of molten salt depletion and environmental contamination, and continuous operation is also possible. The economy can be improved.
- FIG. 1 is an explanatory view showing an example of a manufacturing apparatus used for carrying out the present invention.
- metal Al, metal fluoride salt, and Sc compound are charged into a reaction vessel, and the reaction system in the reaction vessel is heated so that the reaction temperature is in the range of 700 to 1050 ° C. Melting and forming a molten metal layer and a molten salt layer, and adjusting the density of the metal fluoride salt to be 70 to 95% of the density of the molten metal Al at the reaction temperature, The molten metal Al layer having a low Sc concentration is formed in the lower part of the reaction system, and the molten salt layer is formed in contact with the upper part of the reaction system. The interface between the molten salt layer and the molten metal layer at this time The following chemical reaction represented by the reaction formula (1) occurs.
- the reaction direction at the interface between the molten salt layer and the molten metal layer shown in the reaction formula (1) is not only the difference in free energy of formation of Sc salt and Al salt, but also Sc 3+ ions and Al in the molten salt layer. It is determined by the activity of 3+ ions and the activity of Sc in the molten metal Al.
- the activity of Sc 3+ ions in the molten salt layer is large, the activity of Al 3+ ions in the molten salt layer and the activity of Sc in the molten metal are small, and the reaction is caused by the difference in the activities.
- the number of moles of Sc that is reduced and alloyed to the molten metal Al is equal to the number of moles of Al 3+ ions that are oxidized from the molten metal Al, ionized, and dissolved in the molten salt layer, Accompanying the reaction, the concentration of Sc metal in the molten metal Al increases and at the same time the concentration of Al 3+ ions in the molten salt layer also increases.
- Such an activity change is a change in a direction in which the reaction stops, and finally, each of the activities reaches an equilibrium state, and the reaction stops, but within the scope of the present invention,
- the activity of each ion involved in the reaction formula (1) is substantially proportional to the concentration of each ion. Accordingly, in order to efficiently produce the Al—Sc alloy by proceeding the reaction of the reaction formula (1) to the right, the Sc 3 in the molten salt layer before the reaction expressed in mol percentage (mol%). + The ion concentration (Sc 3+ concentration) is kept high, while the Al 3+ ion concentration (Al 3+ concentration) is kept low, and the molten metal before the reaction expressed in mol percentage (mol%). It is necessary to keep the Sc concentration (Sc concentration) in the layer low.
- the reaction temperature of the reaction system is set to 700 to 1050 ° C., and a molten salt layer having a melting point lower than the reaction temperature is provided in the reaction vessel.
- a molten metal layer in a molten state at the reaction temperature is provided in contact with the molten salt layer at the bottom of the molten salt layer in the reaction vessel, and an Sc compound is charged into the molten salt layer, dissolved, and melted.
- the molten salt layer exists above the molten metal layer, oxidation of the reaction product Al—Sc alloy is prevented without making the reaction system an inert gas atmosphere or a vacuum atmosphere.
- the reaction temperature of the reaction system is 700 to 1050 ° C., evaporation from the molten salt layer can be suppressed as much as possible, and the risk of depletion of the molten salt and environmental pollution is reduced.
- the reaction to the right side of the reaction formula (1) is such that the Sc 3+ concentration in the molten salt layer is maintained high, the Sc concentration in the molten metal Al is maintained low, and the molten salt layer If the formed Al 3+ ions form a compound having low solubility in the molten salt, the concentration of Al 3+ in the molten salt layer does not increase, so that the Al 3+ ion continuously turns to the right.
- the reaction formula (1) depends on the Al 3+ concentration and the Sc 3+ concentration in the molten salt layer, but the type of molten salt and Sc as a raw material Since the concentration varies depending on the type of compound, reaction temperature, and the like, even if the concentration of these ions is the same, the Sc concentration finally transferred into the molten metal layer and incorporated as an alloy element is different.
- the target Sc of the alloy element Sc in the Al—Sc alloy after the reaction which is the production purpose, is used.
- the following relational expression (2) shows the relationship between the concentration F Sc , the Sc 3+ concentration P Sc in the molten salt layer as the raw material, and the Sc concentration C Sc of the rare earth metal in the molten metal Al before the reaction. It is necessary to maintain it. That is, in the reaction system of the present invention, by adopting the conditions as shown in the following relational expression (2), the Sc compound in the molten salt layer is efficiently reacted with the molten metal Al and alloyed. An Al—Sc alloy can be produced. 0.3 ⁇ (F Sc ⁇ C Sc ) / P Sc ⁇ 1.5 (2)
- FIG. 1 shows a schematic view of an example of a production apparatus for carrying out the method for producing an Al—Sc alloy of the present invention.
- This production apparatus comprises a reaction vessel 14 and a heating furnace 10 that surrounds the reaction vessel 14 and incorporates a heater 12, and the heater 12 can heat the reaction vessel 14 to at least 1050 ° C.
- the reaction vessel 14 and the heating furnace 10 are made of a material capable of withstanding a temperature of at least 1050 ° C., and the reaction vessel 14 is provided with a reaction vessel 14 for stirring the reaction system so that the molten metal layer does not come into contact with air if necessary. Further, a stirring means (not shown) such as a stirring blade is provided.
- a metal fluoride salt made of a mixture containing the above LiF and NaF in a weight ratio (LiF: NaF) in the range of 7: 5 to 8: 5 is placed in the reaction vessel 14.
- the mixture is heated to a reaction temperature selected from 700 to 1050 ° C. and melted to form a molten salt layer 16, and metal Al is charged into the reaction vessel 14 and heated to the reaction temperature and melted.
- a molten metal layer 18 is made to coexist with the molten salt layer 16.
- the melting point of the metal Al is 660 ° C., and the densities of the molten metal Al at 760 ° C. and 980 ° C.
- the density of the molten mixed salt obtained by melting [1.99 kg / dm 3 (760 ° C.), 1.88 kg / dm 3 (980 ° C.)] is 84% and 82% of the molten metal Al, respectively.
- the molten salt layer 16 and the molten metal layer 18 are separated, and the molten salt layer 16 becomes the upper layer and the molten metal layer 18 becomes the lower layer.
- the Sc compound is charged into the reaction vessel 14 and dissolved in the molten salt layer 16, and Sc 3+ ions are introduced into the molten salt layer 16.
- the recovery-purpose Al—Sc alloy is an Al-1.2 mol% Sc alloy, the recovery amount of the alloy is 1.0 mol, and no Sc is contained in the molten metal layer 18 as a raw material.
- the Sc 3+ concentration in the molten salt layer 16 increases as the Sc compound charged in the reaction vessel 14 is dissolved, and at the same time, the density of the molten salt layer 16 increases. If the concentration of Sc 3+ is up to about 5 mol%, the increase in density is up to about 0.02 kg / dm 3 , and this increase in density (0.02 kg / dm 3 ) is the density of molten metal Al. Since the density of the molten salt layer 16 is 70 to 95% of the density of the molten metal layer 18, the density of the molten salt layer 16 exceeds the density of the molten metal layer 18, Inside the reaction vessel 14, the molten metal layer 18 is not exposed to the upper part of the molten salt layer 16 and comes into contact with air.
- the Al 3+ ions generated by the chemical reaction of the reaction formula (1) are dissolved in the molten salt layer 16, thereby increasing the concentration of Al 3+ in the molten salt layer 16.
- the molten metal layer 18 that is in the lower part and is in contact with the molten salt layer is within the range up to its solubility limit and satisfies the relational expression (2) with respect to the Al 3+ concentration in the molten salt layer 16. Sc is melted to such a value that a molten Al—Sc alloy is formed, and the molten metal Al gradually becomes a molten Al—Sc alloy.
- such a chemical reaction occurs at 700 to 1050 ° C., and the density of the molten salt is lower than the density of the molten metal Al within a predetermined range.
- the surface of the metal layer 18 is protected by the molten salt layer 16, and oxidation of the reaction product Al—Sc alloy can be prevented without using an inert gas atmosphere or a vacuum atmosphere.
- the density of the molten salt layer 16 decreases with the progress of the reaction, and on the other hand, the density of the molten metal layer 18 increases. There is no need to take measures such as stopping energization to adjust the density (or specific gravity) of each layer during the chemical reaction, and the operation is simple and easy.
- the molten metal layer 18 is sampled from the reaction vessel.
- the molten metal layer 18 is external to the reaction vessel 14. As long as it can be transported to the surface, it is not particularly limited, and it can be appropriately carried out by a conventionally known method or the like.
- a molten Al—Sc alloy can be continuously produced.
- the metal Al and the Sc compound are newly charged into the reaction vessel 14 while keeping the reaction vessel 14 within a predetermined reaction temperature range.
- the molten salt layer 16 remaining in the reaction vessel 14 may be melted.
- the Sc compound newly charged in the reaction vessel 14 dissolves in the molten salt of the molten salt layer 16 to generate Sc 3+ ions, and these Sc 3+ ions are simultaneously charged into the reaction vessel 14.
- reaction formula (1) proceeds again to alloy the molten metal Al to form a molten Al-Sc alloy.
- the Al 3+ concentration in the molten salt layer 16 gradually increases.
- the molten salt layer 16 Al 3+ ions are oxidized to Al 2 O 3 , reacting with almost no dissolution in both the molten metal layer 18 which is a molten Al-Sc alloy and the molten salt layer 16 which is a molten metal fluoride salt. Since it is separated from both the molten metal layer 18 and the molten salt layer 16 inside the container 14, it can be easily discharged out of the reaction system. In other words, if Sc 2 O 3 is used as the Sc compound, the side reaction product Al 2 O 3 can be easily discharged out of the reaction system, making it easier to operate continuous production of Al—Sc alloys. Can be.
- Example 1 A metal fluoride salt obtained by mixing LiF and NaF in the amounts shown in Table 1 was charged into a reaction vessel, heated to 960 ° C., melted to form a molten salt layer, and then shown in Table 2. An amount of metal Al was charged into the reaction vessel and melted to form a molten metal layer. These molten salt layer and molten metal layer existed in the reaction vessel in a state where they were in contact with each other while the molten metal layer was separated into the lower layer and the molten salt layer was separated into the upper layer.
- the molten metal layer was collected and analyzed. As shown in Table 3, the molten metal layer contained 0.063 mol of Sc. According to the comparison with the amount of Al, This corresponds to an Al-1.57 mass% Sc alloy, and the value of (F Sc -C Sc ) / P Sc at this time was 0.790. After the chemical reaction, solid Al 2 O 3 was formed on the upper surface of the molten salt layer.
- Example 2 After the reaction system was configured in the same manner as in Example 1, it was held at 960 ° C. for 15 minutes, then cooled to 760 ° C., and then held at 760 ° C. for 180 minutes with stirring to such an extent that the molten metal layer did not come into contact with air. Then, the reaction was performed in the same manner as in Example 1 except that the chemical reaction of the reaction formula (1) was performed. After completion of the reaction, a molten metal layer was collected and analyzed in the same manner as in Example 1.
- the molten metal layer contained 0.070 mol of Sc, and the amount of Al By comparison, this corresponds to an Al-1.74 mass% Sc alloy and the value of (F Sc —C Sc ) / P Sc was 0.878. After the chemical reaction, solid Al 2 O 3 was formed on the upper surface of the molten salt layer.
- Example 3 Example 1 except that the molten salt layer is half the amount of Example 1, the metal Al is the same amount as Example 1, and Sc 2 O 3 as the Sc compound is half the amount of Example 1.
- the molten metal layer was collected and analyzed under the same conditions as in Table 3, as shown in Table 3, the molten metal layer contained 0.027 mol of Sc. According to the comparison with the Al amount, This corresponds to an Al-0.68 mass% Sc alloy, and the value of (F Sc -C Sc ) / P Sc was 0.339. After the chemical reaction, solid Al 2 O 3 was formed on the upper surface of the molten salt layer.
- Example 4 The metal fluoride salt obtained by mixing LiF and NaF in the amounts shown in Table 1 was charged into the reaction vessel to form a molten salt layer. As shown in Table 2, 6.671 moles of metal Al. Was added to the reaction vessel to form a molten metal layer, and as shown in Table 2, the reaction system was constructed by charging 0.160 mol of ScF 3 as the Sc compound. The reaction of reaction formula (1) was carried out. After completion of the reaction, a molten metal layer was collected and analyzed in the same manner as in Example 1. As shown in Table 3, the molten metal layer contained 0.079 mol Sc, By comparison, this corresponds to an Al-1.95 mass% Sc alloy and the value of (F Sc —C Sc ) / P Sc was 1.469. Furthermore, no solid suspension was observed on the upper surface of the molten salt layer after the chemical reaction.
- Example 1 The reaction system was constructed and reacted under the same conditions as in Example 1 except that the metal Al in Example 1 was changed to an Al-3.00 mass% Sc alloy consisting of 6.471 mol of Al and 0.120 mol of Sc. It was.
- the Sc amount was 0.098 mol, which was less than the content before the reaction, By comparison, this corresponds to Al-2.45 mass% Sc, and the value of (F Sc -C Sc ) / P Sc was -0.323.
- solid Al 2 O 3 was formed on the upper surface of the molten salt layer. The reason why (F Sc -C Sc ) / P Sc became negative was that the Sc concentration in the molten metal layer was already high when 0.080 mol of Sc 2 O 3 was charged as the Sc compound. it is conceivable that.
- Example 5 The reaction system was used under the same conditions as in Example 1 except that LiF and NaF in the amounts shown in Table 1 and metal Al in the amounts shown in Table 2 were used, and 0.160 mol of Sc 2 O 3 was used as the Sc compound. Was made to react.
- the molten metal layer after completion of the reaction was collected and analyzed. As shown in Table 3, the molten metal layer contained 0.127 mol of Sc, which was compared with the amount of Al. For example, this corresponds to an Al-3.10 mass% Sc alloy and the value of (F Sc —C Sc ) / P Sc was 0.980.
- solid Al 2 O 3 was formed on the upper surface of the molten salt layer.
- Example 6 As shown in Tables 1 and 2, first, the reaction system was constituted and reacted under the same conditions as in Example 5, and as shown in Table 3, 0.124 mol of Sc was contained in the molten metal layer. Thus, a molten Al—Sc alloy layer corresponding to the Al-3.02 mass% Sc alloy was formed. At this time, the value of (F Sc -C Sc ) / P Sc was 0.957, and solid Al 2 O 3 was formed on the upper surface of the molten salt layer after completion of the chemical reaction.
- the obtained molten metal layer was collected and analyzed. As shown in Table 3, the third molten metal layer contained 0.076 mol of Sc. According to the comparison with the Al content, this corresponds to the Al-1.89 mass% Sc alloy, and the value of (F Sc -C Sc ) / P Sc was 0.893. After the completion of the third chemical reaction, solid Al 2 O 3 was formed on the upper surface of the molten salt layer.
- Example 7 A metal fluoride salt obtained by mixing LiF and NaF in the amounts shown in Table 1 was heated to 960 ° C. in a reaction vessel and melted to form a molten salt layer. Subsequently, as shown in Table 2, 6 .671 mol of metal Al was charged into the reaction vessel and melted to form a molten metal layer, and 0.080 mol of Sc 2 O 3 was charged as the Sc compound while maintaining the reaction vessel at 960 ° C. Then, the mixture was held at 960 ° C. for 15 minutes with stirring to such an extent that the molten metal layer did not come into contact with air, and the chemical reaction of reaction formula (1) was carried out.
- Example 8 As shown in Table 1, a metal fluoride salt consisting of a mixture of 1.700 moles NaF, 0.104 moles CaF 2 and 0.831 moles AlF 3 was used and heated to 960 ° C. in a reaction vessel, As shown in Table 2, 6.671 mol of metal Al was charged into the reaction vessel and melted to form a molten metal layer, and the reaction vessel was further heated to 960 ° C. While being held, 0.094 mol of Sc 2 O 3 was charged as the Sc compound, and held at 980 ° C. for 180 minutes with stirring to such an extent that the molten metal layer did not come into contact with air. Carried out.
- a metal fluoride salt consisting of a mixture of 2.316 moles LiF, 1.252 moles NaF, 0.323 moles KF and 0.321 moles BaF 2 was used in a reaction vessel. The mixture was heated to 960 ° C. and melted to form a molten salt layer. Subsequently, as shown in Table 2, 6.671 mol of metal Al was charged into the reaction vessel and melted to form a molten metal layer. In the reaction vessel, the molten metal layer and the molten salt layer were separated from each other, but the molten metal layer was exposed as an upper layer above the molten salt layer and was in contact with air.
- the metal layer was collected and analyzed. As shown in Table 3, the metal layer contained 0.032 mol of Sc. According to the comparison with the Al amount, This corresponds to an Al-0.87 mass% Sc alloy, and the value of (F Sc -C Sc ) / P Sc was 0.283. The reason why the value of (F Sc -C Sc ) / P Sc was less than 0.3 is considered to be that the molten metal layer was exposed to the upper part of the molten salt layer and contacted with air to be oxidized.
- the metal layer contained 0.011 mol of Sc. According to the comparison with the amount of Al, Corresponds to an Al-0.28 mass% Sc alloy, and the value of (F Sc -C Sc ) / P Sc was 0.216. The reason why the value of (F Sc -C Sc ) / P Sc was less than 0.3 is considered to be because the Al 3+ concentration in the molten salt layer was high.
- the metal layer contained 0.013 mol of Sc.
- the metal layer contained 0.013 mol of Sc.
- the value of (F Sc -C Sc ) / P Sc was 0.229.
- the value of (F Sc -C Sc ) / P Sc was less than 0.3 because the Sc compound charged in the molten salt layer was ScF 3 , so that it was soluble in the molten salt by a chemical reaction. This is considered to be because the AlF 3 was produced as a side reaction product and the Sc 3+ concentration in the molten salt layer was relatively lowered by the production of the AlF 3 .
- the present invention does not require equipment for heating in an inert gas atmosphere or a vacuum atmosphere, a reducing agent such as metal Ca, equipment for molten salt electrolysis, and electric power, and heating up to 1050 ° C.
- a reducing agent such as metal Ca
- the manufacturing process is simple and simple, and can be suitably used as a method for manufacturing an Al—Sc alloy.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
前記反応系の反応温度を700~1050℃の範囲内とし、また、前記金属フッ化物塩として、その融点が前記反応温度よりも低く、かつ、その密度が前記反応系の反応温度において溶融金属アルミニウムの密度の70~95%の範囲内である金属フッ化物塩を使用し、前記反応容器内の反応系において、前記溶融塩層が上層で前記溶融金属層が下層となるようにしたことを特徴とするAl-Sc系合金の製造方法である。
Sc3+/(s)+Al/(m) ⇔ Sc/(m)+Al3+/(s)……(1)
〔ただし、反応式(1)において、溶融塩層内の元素又はイオンを/(s)と示し、また、溶融金属層内のもの元素又はイオンを/(m)と示す。〕
0.3≦(FSc-CSc)/PSc≦1.5……(2)
図1に、本発明のAl-Sc系合金の製造方法を実施する製造装置の一例に係る模式図が示されている。この製造装置は、反応容器14と、前記反応容器14を囲繞し、加熱器12を内蔵する加熱炉10とからなり、加熱器12は反応容器14を少なくとも1050℃まで加熱することができ、また、反応容器14及び加熱炉10は少なくとも1050℃の温度に耐えられる材質で形成されているほか、反応容器14には、必要により、溶融金属層が空気と接触しない程度に反応系を撹拌するために、攪拌翼等の図示外の撹拌手段が設けられている。
表1に示す量のLiFとNaFとを混合して得られた金属ふっ化物塩を反応容器内に装入し、960℃に加熱し、溶融させて溶融塩層とし、続いて表2に示す量の金属Alを反応容器内に装入し、溶融させて溶融金属層とした。これら溶融塩層と溶融金属層は、前記反応容器内に溶融金属層が下層に、また、溶融塩層が上層に分離しつつ互いに接触した状態で存在していた。
実施例1と同様にして反応系を構成した後、960℃で15分保持し、次いで760℃まで冷却した後、溶融金属層が空気に接触しない程度に撹拌しながら760℃で180分間保持して反応式(1)の化学反応をさせた以外は、実施例1と同様に実施した。
反応終了後、実施例1と同様に溶融金属層を採取し、分析したところ、表3に示すように、前記溶融金属層には0.070モルのScが含有されており、Al量との対比によれば、これはAl-1.74mass%Sc合金に相当し、また、(FSc-CSc)/PScの値は0.878であった。化学反応終了後、溶融塩層の上部表面には固体のAl2O3が生成していた。
溶融塩層を実施例1の半分の量とし、金属Alを実施例1と同じ量とし、また、Sc化合物としてのSc2O3を実施例1の半分の量とした以外は、実施例1と同じ条件で反応させ、溶融金属層を採取、分析したところ、表3に示すように、前記溶融金属層には0.027モルのScが含有されており、Al量との対比によれば、これはAl-0.68mass%Sc合金に相当し、また、(FSc-CSc)/PScの値は0.339であった。化学反応終了後、溶融塩層の上部表面には固体のAl2O3が生成していた。
表1に示す量のLiFとNaFとを混合して得られた金属ふっ化物塩を反応容器内に装入して溶融塩層とし、また、表2に示すように6.671モルの金属Alを反応容器内に装入して溶融金属層とし、更に、表2に示すようにSc化合物として0.160モルのScF3を装入して反応系を構成した以外は、実施例1と同様にして反応式(1)の反応を行った。
反応終了後、実施例1と同様に溶融金属層を採取し、分析したところ、表3に示すように、前記溶融金属層には0.079モルのScが含有されており、Al量との対比によれば、これはAl-1.95mass%Sc合金に相当し、また、(FSc-CSc)/PScの値は1.469であった。更に、化学反応終了後の溶融塩層の上部表面に固体の浮遊物は観察されなかった。
実施例1の金属Alを6.471モルのAlと0.120モルのScからなるAl-3.00mass%Sc系合金に変更した以外は、実施例1と同じ条件で反応系を構成し反応させた。
反応終了後の溶融金属層を採取し、分析したところ、表3に示されているように、Sc量は0.098モルであって反応前の含有量より減少しており、Al量との対比によれば、これはAl-2.45mass%Scに相当し、また、(FSc-CSc)/PScの値は-0.323であった。化学反応終了後、溶融塩層の上部表面には、固体のAl2O3が生成していた。(FSc-CSc)/PScが負の値となったのは、Sc化合物として0.080モルのSc2O3を装入した時点において、溶融金属層内のSc濃度が既に高かったためと考えられる。
表1に示す量のLiF及びNaFと表2に示す量の金属Alを用い、また、Sc化合物として0.160モルのSc2O3を用いた以外は、実施例1と同じ条件で反応系を構成し反応させた。
反応終了後の溶融金属層を採取し、分析したところ、表3に示されているように、前記溶融金属層には0.127モルのScが含有されており、Al量との対比によれば、これはAl-3.10mass%Sc合金に相当し、また、(FSc-CSc)/PScの値は0.980であった。化学反応終了後、溶融塩層の上部表面には固体のAl2O3が生成していた。
表1及び表2に示すように、初めに、上記実施例5と同じ条件で反応系を構成して反応させ、表3に示すように、溶融金属層に0.124モルのScが含有されてAl-3.02mass%Sc合金に相当する溶融Al-Sc系合金層を形成させた。このとき、(FSc-CSc)/PScの値は0.957であり、化学反応終了後の溶融塩層の上部表面には固体のAl2O3が生成していた。
表1に示す量のLiFとNaFとを混合して得られた金属ふっ化物塩を反応容器内で960℃に加熱し、溶融して溶融塩層とし、続いて表2に示すように、6.671モルの金属Alを反応容器内に装入し、溶融させて溶融金属層とし、更に、反応容器内を960℃に保持しつつSc化合物として0.080モルのSc2O3を装入し、前記溶融金属層が空気に接触しない程度に撹拌しながら960℃に15分間保持し、反応式(1)の化学反応を実施した。
表1に示すように、1.700モルのNaF、0.104モルのCaF2及び0.831モルのAlF3の混合物からなる金属ふっ化物塩を用い、反応容器内で960℃に加熱し、溶融して溶融塩層とし、続いて表2に示すように、6.671モルの金属Alを反応容器内に装入して溶融させ、溶融金属層とし、更に、反応容器内を960℃に保持しつつSc化合物として0.094モルのSc2O3を装入し、前記溶融金属層が空気に接触しない程度に撹拌しながら980℃で180分間保持し、反応式(1)の化学反応を実施した。
表1に示すように、2.316モルのLiF、1.252モルのNaF、0.323モルのKF及び0.321モルのBaF2の混合物からなる金属ふっ化物塩を用い、反応容器内で960℃に加熱し、溶融して溶融塩層とし、続いて表2に示すように、6.671モルの金属Alを反応容器内に装入し、溶融させて溶融金属層とした。前記反応容器内において、前記溶融金属層と溶融塩層は互いに分離したが、溶融金属層が溶融塩層の上部に上層として露出し、空気と接触していた。
表1に示すように、2.333モルのNaF、2.091モルのCaF2及び2.333モルのAlF3の混合物からなる金属ふっ化物塩を用い、反応容器内で960℃に加熱し、溶融して溶融塩層とし、続いて表2に示すように、6.671モルの金属Alを反応容器内に装入し、溶融させて溶融金属層とした。前記反応容器内において、前記溶融金属層と溶融塩層は互いに分離し、溶融金属層が下層として溶融塩層の下部に該溶融塩層と接触して存在していた。
表1に示すように、2.203モルのLiF、1.478モルのNaF及び0.428モルのAlF3の混合物からなる金属ふっ化物塩を用い、反応容器内で960℃に加熱し、溶融して溶融塩層とし、続いて表2に示すように、6.671モルの金属Alを反応容器内に装入し、溶融させて溶融金属層とした。前記反応容器内において、前記溶融金属層と溶融塩層は互いに分離し、溶融金属層が下層として溶融塩層の下部に該溶融塩層と接触して存在していた。
Claims (5)
- 金属アルミニウム(Al)と、アルカリ金属ふっ化物、アルカリ土類金属ふっ化物及びふっ化アルミニウムからなる群から選ばれた1種又は2種以上の金属ふっ化物塩と、スカンジウム(Sc)の酸化物及び/又はふっ化物塩からなるスカンジウム化合物とを反応容器内に装入し、反応容器内の前記金属アルミニウム(Al)と前記金属ふっ化物塩と前記スカンジウム化合物とからなる反応系を反応温度まで昇温させて溶融金属アルミニウムからなる溶融金属層と前記金属ふっ化物塩及びスカンジウム化合物が溶融した溶融塩層とを形成し、前記溶融塩層側に生成したスカンジウムイオン(Sc3+)を溶融金属層側に移行させてAl-Sc系合金を製造する方法であって、
前記反応系の反応温度を700~1050℃の範囲内とし、また、
前記金属ふっ化物塩として、その融点が前記反応温度よりも低く、かつ、その密度が前記反応系の反応温度において溶融金属アルミニウムの密度の70~95%の範囲内である金属フッ化物塩を使用し、
前記反応容器内の反応系において、前記溶融塩層が上層で前記溶融金属層が下層となるようにしたことを特徴とするAl-Sc系合金の製造方法。 - 金属アルミニウム(Al)と金属フッ化物塩とを反応容器内に装入し、反応温度まで昇温させて溶融金属層と溶融塩層とを形成した後に、前記溶融塩層内にスカンジウム化合物を添加し、この溶融塩層内にスカンジウムイオン(Sc3+)を生成させることを特徴とする請求項1に記載のAl-Sc系合金の製造方法。
- 前記金属フッ化物塩が、ふっ化リチウムとふっ化ナトリウムとの混合物であることを特徴とする請求項1又は2に記載のAl-Sc系合金を製造方法。
- モル百分率(mol%)で表されたAl-Sc系合金中の目標Sc濃度をFScとし、モル百分率で表された溶融塩層中のSc3+濃度をPScとし、また、モル百分率で表された溶融金属層中のSc濃度をCScとしたとき、反応容器内の反応系が0.3≦(FSc-CSc)/PSc≦1.5の関係を満たすことを特徴とする請求項1~3のいずれかに記載のAl-Sc系合金の製造方法。
- 請求項1~4のいずれか1項に記載のAl-Sc系合金の製造方法によって得られたAl-Sc系合金。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/424,348 US9422611B2 (en) | 2013-06-26 | 2013-06-26 | Al—Sc alloy manufacturing method |
JP2013544960A JP5445725B1 (ja) | 2013-06-26 | 2013-06-26 | Al−Sc合金の製造方法 |
PCT/JP2013/067503 WO2014207834A1 (ja) | 2013-06-26 | 2013-06-26 | Al-Sc合金の製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2013/067503 WO2014207834A1 (ja) | 2013-06-26 | 2013-06-26 | Al-Sc合金の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014207834A1 true WO2014207834A1 (ja) | 2014-12-31 |
Family
ID=50614405
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/067503 WO2014207834A1 (ja) | 2013-06-26 | 2013-06-26 | Al-Sc合金の製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9422611B2 (ja) |
JP (1) | JP5445725B1 (ja) |
WO (1) | WO2014207834A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104928507A (zh) * | 2015-07-01 | 2015-09-23 | 广西冶金研究院 | 一种混合熔盐体系中铝热还原制备铝钪中间合金的方法 |
KR20180058426A (ko) * | 2016-11-24 | 2018-06-01 | 연세대학교 산학협력단 | 스칸듐 합금 및 이의 제조방법 |
CN110306072A (zh) * | 2019-07-29 | 2019-10-08 | 中国恩菲工程技术有限公司 | 铝钪合金及其制备方法 |
JP2021515851A (ja) * | 2018-03-15 | 2021-06-24 | インフィニアム インコーポレイテッド | アルミニウム−スカンジウム合金の製造方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2013201572B2 (en) * | 2013-03-15 | 2014-12-11 | Commonwealth Scientific And Industrial Research Organisation | Production of Aluminium-Scandium Alloys |
JP5907186B2 (ja) * | 2014-01-27 | 2016-04-26 | 住友金属鉱山株式会社 | スカンジウム濃縮物回収方法 |
RU2593246C1 (ru) * | 2015-04-22 | 2016-08-10 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Способ получения лигатуры алюминий-скандий |
KR101724288B1 (ko) * | 2015-07-17 | 2017-04-10 | 재단법인 포항산업과학연구원 | 고순도 알루미늄-스칸듐 합금 제조 방법 |
KR102562722B1 (ko) * | 2016-02-01 | 2023-08-03 | 재단법인 포항산업과학연구원 | 전해용 양극, 이를 포함하는 전해조, 및 상기 전해조를 이용한 전해 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04235231A (ja) * | 1991-01-05 | 1992-08-24 | Aluminum Co Of America <Alcoa> | 軽金属−希土類金属合金を製造する方法 |
JPH1150170A (ja) * | 1997-08-05 | 1999-02-23 | Showa Alum Corp | アルミニウム合金の製造装置およびこれを用いたアルミニウム合金の製造方法 |
JP2003171724A (ja) * | 2001-12-07 | 2003-06-20 | Aomori Prefecture | Al−Sc母合金の製造法およびその方法によって得られたAl−Sc母合金 |
JP2007254822A (ja) * | 2006-03-23 | 2007-10-04 | Taiheiyo Kinzoku Kk | スカンジウム含有合金の製造方法およびこの方法により得られたスカンジウム含有合金 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2555611B1 (fr) | 1983-11-25 | 1986-04-18 | Rhone Poulenc Spec Chim | Procede de preparation d'alliages d'aluminium et de terres rares |
JP2876761B2 (ja) | 1990-09-21 | 1999-03-31 | 三菱マテリアル株式会社 | 希土類金属の粉末を製造する方法 |
JPH06172887A (ja) | 1992-12-08 | 1994-06-21 | Mitsubishi Kasei Corp | アルミニウム合金の製造方法 |
JP2001348637A (ja) | 2000-06-05 | 2001-12-18 | Hitachi Cable Ltd | アルミニウム合金材及びそれを用いた配線材の製造方法 |
RU2213795C1 (ru) * | 2001-11-12 | 2003-10-10 | Махов Сергей Владимирович | Способ получения лигатуры алюминий-скандий (варианты) |
CN100410400C (zh) * | 2004-11-09 | 2008-08-13 | 湖南稀土金属材料研究院 | 铝热还原制备铝钪合金的方法 |
FR2978060B1 (fr) * | 2011-07-21 | 2016-02-12 | Commissariat Energie Atomique | Procede et dispositif de mise en contact sans melange et a haute temperature de deux liquides non miscibles avec chauffage et brassage par induction |
-
2013
- 2013-06-26 WO PCT/JP2013/067503 patent/WO2014207834A1/ja active Application Filing
- 2013-06-26 US US14/424,348 patent/US9422611B2/en active Active
- 2013-06-26 JP JP2013544960A patent/JP5445725B1/ja not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04235231A (ja) * | 1991-01-05 | 1992-08-24 | Aluminum Co Of America <Alcoa> | 軽金属−希土類金属合金を製造する方法 |
JPH1150170A (ja) * | 1997-08-05 | 1999-02-23 | Showa Alum Corp | アルミニウム合金の製造装置およびこれを用いたアルミニウム合金の製造方法 |
JP2003171724A (ja) * | 2001-12-07 | 2003-06-20 | Aomori Prefecture | Al−Sc母合金の製造法およびその方法によって得られたAl−Sc母合金 |
JP2007254822A (ja) * | 2006-03-23 | 2007-10-04 | Taiheiyo Kinzoku Kk | スカンジウム含有合金の製造方法およびこの方法により得られたスカンジウム含有合金 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104928507A (zh) * | 2015-07-01 | 2015-09-23 | 广西冶金研究院 | 一种混合熔盐体系中铝热还原制备铝钪中间合金的方法 |
KR20180058426A (ko) * | 2016-11-24 | 2018-06-01 | 연세대학교 산학협력단 | 스칸듐 합금 및 이의 제조방법 |
KR101927379B1 (ko) * | 2016-11-24 | 2019-03-12 | 연세대학교 산학협력단 | 스칸듐 합금 및 이의 제조방법 |
JP2021515851A (ja) * | 2018-03-15 | 2021-06-24 | インフィニアム インコーポレイテッド | アルミニウム−スカンジウム合金の製造方法 |
JP7361058B2 (ja) | 2018-03-15 | 2023-10-13 | エフイーエー マテリアルズ エルエルシー | アルミニウム-スカンジウム合金の製造方法 |
US11970782B2 (en) | 2018-03-15 | 2024-04-30 | Fea Materials Llc | Method of aluminum-scandium alloy production |
CN110306072A (zh) * | 2019-07-29 | 2019-10-08 | 中国恩菲工程技术有限公司 | 铝钪合金及其制备方法 |
CN110306072B (zh) * | 2019-07-29 | 2021-05-11 | 中国恩菲工程技术有限公司 | 铝钪合金及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014207834A1 (ja) | 2017-02-23 |
US20150232965A1 (en) | 2015-08-20 |
JP5445725B1 (ja) | 2014-03-19 |
US9422611B2 (en) | 2016-08-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5445725B1 (ja) | Al−Sc合金の製造方法 | |
CN108138343B (zh) | 利用电解还原和电解精炼工序的金属精炼方法 | |
KR101163375B1 (ko) | 원광 금속환원 및 전해정련 일관공정에 의한 원자로급 지르코늄 친환경 신 제련공정 | |
WO2010137555A1 (ja) | 精製された金属又は半金属の製造方法 | |
EP3368477A1 (en) | Method for the enrichment and separation of silicon crystals from a molten metal for the purification of silicon | |
AU2019236275B2 (en) | Method of aluminum-scandium alloy production | |
KR101878652B1 (ko) | 전해환원 및 전해정련 일관공정에 의한 금속 정련 방법 | |
WO2022092231A1 (ja) | 再生アルミニウムの製造方法、製造装置、製造システム、再生アルミニウム、及び、アルミニウム加工物 | |
US20240026555A1 (en) | Reduction system and method for high-melting point metal oxides, using liquid metal crucible | |
RU2401874C2 (ru) | Способ волкова для производства химически активных металлов и устройство для его осуществления | |
JP2022058350A (ja) | 反応性金属の電解生成 | |
JP2926280B2 (ja) | 稀土類−鉄合金の製造方法 | |
CN111187916A (zh) | 一种利用工业钛渣制备高纯钛的方法 | |
CN103132108B (zh) | 熔盐体系中电解制备耐热镁铝钕合金的方法 | |
JP5236897B2 (ja) | シリコンの製造方法 | |
US20240002974A1 (en) | Reduction method and system for high-melting-point metal oxide, using fluoride-based electrolytes | |
JP2013036075A (ja) | インジウム又はインジウム合金の精製方法 | |
JPS63118089A (ja) | チタン,チタン合金の製造方法 | |
Sokhanvaran et al. | Advances in Electrometallurgy for Sustainable Metal Production | |
JP2024011006A (ja) | 高融点金属薄膜の製造方法 | |
JP2008290908A (ja) | 固体シリコンの製造方法 | |
JPS59104441A (ja) | Ca−Al合金の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013544960 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13887776 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14424348 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13887776 Country of ref document: EP Kind code of ref document: A1 |