CN110205652B - Preparation method and application of copper-scandium intermediate alloy - Google Patents

Preparation method and application of copper-scandium intermediate alloy Download PDF

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CN110205652B
CN110205652B CN201910407398.3A CN201910407398A CN110205652B CN 110205652 B CN110205652 B CN 110205652B CN 201910407398 A CN201910407398 A CN 201910407398A CN 110205652 B CN110205652 B CN 110205652B
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scandium
copper
molten salt
alloy
crucible
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CN110205652A (en
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李斌川
马成贵
陈建设
韩庆
孔亚鹏
刘奎仁
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Northeastern University China
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    • 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
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions

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Abstract

The invention discloses a preparation method of a copper-scandium intermediate alloy, which is characterized in that in a molten salt electrolyte containing scandium, a metal copper electrode is taken as a consumable cathode, graphite is taken as an anode, and the copper-scandium intermediate alloy is prepared through molten salt electrolysis; the copper-scandium master alloy prepared by the method is used for preparing scandium-containing aluminum alloy or other scandium-containing alloys. The preparation method provided by the invention has the advantages of simple process, no pollution and low production cost, and the prepared copper-scandium intermediate alloy has scandium content of 10-75%, and can be used for preparing various scandium-containing alloys.

Description

Preparation method and application of copper-scandium intermediate alloy
Technical Field
The invention relates to the technical field of alloy preparation, in particular to a preparation method and application of a copper-scandium intermediate alloy.
Background
Scandium has an atomic number of 21, and belongs to the III subgroup with lanthanide rare earth metals and to 3d type transition metals with titanium, vanadium, chromium and the like in the periodic table. Scandium metal is an excellent modifier for cast aluminum alloys and also an excellent modifier for iron. At present, a large amount of metal scandium is applied to preparing aluminum-scandium alloy, and trace metal scandium (0.1-0.4%) is added into the aluminum alloy, so that alloy grains can be refined, and the strength, the plastic toughness, the high temperature resistance, the corrosion resistance and the like of the aluminum alloy are obviously improved. The comprehensive performance of the scandium-containing aluminum alloy is obviously superior to that of the traditional aluminum alloy, and the scandium-containing aluminum alloy is widely applied to the advanced scientific and technological fields of aerospace, military industry and the like.
As simple scandium has active chemical property and has high melting point (1541 ℃) and larger difference with the melting point of aluminum (660 ℃), scandium-containing aluminum alloy is difficult to prepare by a direct casting method. During the production of aluminium-scandium alloys in industry, scandium is usually added to the alloy in the form of a master alloy. At present, the preparation methods of the aluminum-scandium master alloy mainly comprise a counter doping method, a metallothermic reduction method and a molten salt electrolysis method.
In the opposite doping method, high-purity scandium and pure aluminum are used as raw materials, in an argon protective atmosphere, the metal scandium with a specific proportion is wrapped by an aluminum foil and then added into an aluminum melt, the mixture is fully stirred, and casting is carried out after heat preservation is carried out for enough time, so that the aluminum-scandium intermediate alloy can be prepared. The aluminum-scandium intermediate alloy with scandium content of 2-4% can be prepared by adopting a counter-doping method, the process is simple, but the counter-doping method needs high-purity metal scandium as a raw material, and the cost is high; the alloy loss is large, and the recovery rate is low; and the melting points of scandium and aluminum have large difference, the components in the alloy are not uniformly distributed, and the quality is poor.
The metallothermic reduction method mainly adopts a scandium fluoride vacuum aluminothermic reduction method, adopts scandium fluoride as a raw material, adopts metallic aluminum as a reducing agent, and prepares the aluminum-scandium intermediate alloy by reduction under vacuum. The scandium content in the intermediate alloy prepared by the method can reach 30%, but the preparation process of the scandium fluoride raw material is complex, the process cannot realize continuous production, and the yield is low.
The molten salt electrolysis method mainly uses scandium oxide or scandium chloride as a raw material and carries out electrolysis in a chloride system or a fluoride system. Wherein, when scandium chloride is used as a raw material, NaCl-KCl-ScCl is mostly adopted3And LiCl-KCl-ScCl3For the electrolyte, liquid aluminum metal is used as a cathode, scandium ions are deposited on the liquid aluminum cathode and alloyed therewith by using suitable electrolysis parameters, and Cl is added to the anode-Is oxidized to generate chlorine. It should be noted that scandium chloride is moisture-absorbing and difficult to transport and store, and chlorine gas generated in the electrolysis process pollutes the environment, so that it is less used in industrial production. When scandium oxide is used as the raw material, the electrolyte used is NaF. AlF3–Sc2O3–ScF3–NaCl，NaF–Sc2O3–ScF3、CaCl2–Sc2O3Or LiF-Sc2O3–ScF3Liquid metal aluminum is mostly adopted as a cathode or Al is added into molten salt2O3So that liquid aluminum is generated at the cathode during electrolysis, and scandium ions are deposited at the cathode and form an intermediate alloy with aluminum during electrolysis. Compared with a counter doping method and a metallothermic reduction method, the aluminum-scandium master alloy prepared by the molten salt electrolysis method has the advantages of uniform components, low production cost, easy continuous production, no need of reducing agent and the like. In the research on preparing scandium master alloy by molten salt electrolysis, aluminum-scandium alloy is basically used as a target productScandium is collected by liquid aluminum, but the melting points of aluminum and scandium are greatly different, so that in the process of preparing an aluminum-scandium alloy through electrolysis, an aluminum melt needs to be overheated to a high degree, scandium diffuses slowly in aluminum, a high-concentration scandium-containing alloy component with uniform components is difficult to form, and the scandium content in the intermediate alloy is low.
Disclosure of Invention
The invention aims to solve the technical problem of low scandium content in the process of preparing scandium master alloy through molten salt electrolysis, and provides a method for preparing a copper-scandium master alloy with high scandium content through electrolysis by using a copper-consumable cathode.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a copper-scandium intermediate alloy comprises the steps of taking a metal copper electrode as a consumable cathode and graphite as an anode in a molten salt electrolyte containing scandium, and preparing the copper-scandium intermediate alloy through molten salt electrolysis.
Further, the molten salt electrolyte comprises the following components in parts by mass: 20-70 parts of LiF and 5-60 parts of ScF30-55 parts of MCl or/and MF, wherein M is one or more of alkali metal elements and alkaline earth metal elements.
Further, a raw material Sc is added to the molten salt electrolyte2O3，Sc2O3The mass of the added salt is 0-30% of the mass of the fused salt.
Further, the temperature of molten salt electrolysis is 875-1100 ℃.
Further, the molten salt electrolysis is carried out, and the cathode current density is controlled to be 0.5-40A/cm2。
Furthermore, a holding crucible is placed below the copper cathode to collect the copper-scandium intermediate alloy product, and the holding crucible is a molybdenum crucible, a tungsten crucible, a tantalum crucible or a graphite crucible.
The copper-scandium master alloy prepared by the method is used for preparing scandium-containing alloys of other metals.
The preparation method of the copper-scandium intermediate alloy provided by the invention has the advantages of simple process, no pollution, wide raw material source and low production cost; the prepared copper-scandium intermediate alloy has low impurity content, the scandium content can reach 10-75% according to the mass ratio of substances, the copper-scandium intermediate alloy can be used for preparing various scandium-containing alloys, and the mechanical properties, strength, plasticity and toughness, high temperature resistance, corrosion resistance and the like of the alloy can be obviously improved.
Detailed Description
A preparation method of a copper-scandium intermediate alloy comprises the steps of taking a metal copper electrode as a consumable cathode and graphite as an anode in a molten salt electrolyte containing scandium, and preparing the copper-scandium intermediate alloy through molten salt electrolysis.
Wherein the molten salt electrolyte component is LiF-ScF3-MCl/MF, M being one or more of alkali metal elements and alkaline earth metal elements, the molten salt electrolyte comprising, in parts by mass: 20-70 parts of LiF and 5-60 parts of ScF30-55 parts of MCl or/and MF. Adding a raw material Sc to the molten salt electrolyte2O3，Sc2O3The mass of the added salt is 0-30% of the mass of the fused salt.
In particular to a preparation method of a copper-scandium master alloy, which is to use Sc2O3The copper rod and the molten salt electrolyte are uniformly mixed, the mixture is contained by a graphite crucible, the graphite crucible is used as an anode, a copper rod is inserted into the molten salt to be used as a cathode, a containing crucible is placed below the copper rod to collect a cathode product, the containing crucible is insulated and separated from the graphite crucible, and the copper-scandium intermediate alloy is prepared by electrolyzing the molten salt.
The temperature of molten salt electrolysis is 875-1100 ℃, and the cathode current density is controlled to be 0.5-40A/cm2
The holding crucible is a molybdenum crucible, a tungsten crucible, a tantalum crucible or a graphite crucible. .
The copper-scandium master alloy prepared by the method is used for preparing scandium-containing alloy. The scandium-containing alloy is added into other metals in the form of master alloy to prepare the scandium-containing alloy.
The melting points of copper and scandium are relatively small in difference, the liquidus line is relatively flat according to a Cu-Sc phase diagram, scandium and copper respectively form 13 percent (mass ratio) of scandium at 865 ℃, 875 ℃ forms 30 percent or 71 percent (mass ratio) of scandium at 890 ℃, and Cu-Sc alloy containing 36.5 percent (mass ratio) of scandium at 890 ℃. Therefore, the invention provides the method which takes scandium fluoride or scandium oxide as the raw materialThe method comprises the steps of preparing a copper-scandium intermediate alloy product with high scandium content by adopting a copper consumable cathode in a fluoride or chloride molten salt electrolyte and electrolyzing by taking graphite as an anode. During electrolysis, scandium ions Sc3+The liquid alloy migrates to a cathode and is reduced to metal scandium on a copper cathode, the metal scandium and the copper form a Cu-Sc alloy, the electrolysis temperature is lower than the melting point of the copper but higher than the melting point of the Cu-Sc alloy, the obtained liquid alloy is separated from the copper cathode and sinks into a holding crucible below the cathode, and the copper cathode exposes a new surface to continue electrolysis. As the electrolysis proceeds, the copper cathode is continuously consumed to form an alloy. By adjusting the electrolysis temperature and the current density, copper-scandium intermediate alloys with different scandium contents can be obtained, and Cu-Sc alloy ingots are obtained after the Cu-Sc alloy in the holding crucible is cast and cooled.
The inventive summary of the present invention is as follows:
1. the cathode is a consumable cathode, the cathode product is liquid, and compared with a solid product, the cathode product has low impurity content and is convenient to process subsequently;
2. compared with the method for producing the aluminum-scandium alloy by adopting liquid cathode aluminum molten salt electrolysis, the scandium content is obviously increased, and the scandium-containing aluminum molten salt electrolysis intermediate alloy is used as an intermediate alloy for aluminum-scandium alloy blending, so that the scandium-containing aluminum molten salt electrolysis intermediate alloy is convenient to apply, the scandium-containing aluminum molten salt electrolysis intermediate alloy can greatly reduce the production scale of the scandium alloy, and the equipment investment and the scandium alloy production cost are saved;
3. the production equipment and mode of rare earth-iron alloy such as dysprosium-iron, terbium-iron and the like can be used for reference, special scandium alloy electrolysis equipment does not need to be developed, and the technology maturity is high.
Example 1 preparation method of copper-scandium master alloy
500g of molten salt and 150g of Sc2O3Uniformly mixing the materials, putting the mixture into a graphite crucible with the diameter of 80mm, wherein the molten salt electrolyte system is 60 parts of ScF according to mass percentage320 parts of LiF and 10 parts of NaF; a molybdenum crucible which is insulated from graphite and has a diameter of 50mm is placed at the center of the bottom of the graphite crucible to serve as a holding crucible; then, the graphite crucible is placed into a furnace and heated to 875 ℃, and after the molten salt is dissolved, a copper rod with the diameter of 20mm is inserted into the molten salt, and the immersion depth is 30 mm; the graphite crucible is used as an anode, the copper bar is used as a cathode for electrolysis, and the current is denseThe degree is 40A/cm2(ii) a And (4) taking out the molybdenum crucible by using crucible tongs after 2h of electrolysis, and casting the collected copper-scandium intermediate alloy liquid into a mould to prepare a copper-scandium intermediate alloy ingot. Through detection, the alloy comprises the following components in percentage by mass: 25% of copper and 75% of scandium.
Embodiment 2 preparation method of copper-scandium master alloy
500g of molten salt and 100g of Sc2O3Uniformly mixing the materials, putting the mixture into a graphite crucible with the diameter of 80mm, wherein the molten salt electrolyte system is 5 parts of ScF according to mass percentage3And 70 parts of LiF; a molybdenum crucible which is insulated from graphite and has a diameter of 50mm is placed at the center of the bottom of the graphite crucible to serve as a holding crucible; then, the graphite crucible is put into a furnace and heated to 1100 ℃, and after the molten salt is melted, a copper rod with the diameter of 20mm is inserted into the molten salt, and the immersion depth is 30 mm; electrolyzing with graphite crucible as anode and copper rod as cathode at current density of 10A/cm2(ii) a And (4) taking out the molybdenum crucible by using crucible tongs after 2h of electrolysis, and casting the collected copper-scandium intermediate alloy liquid into a mould to prepare a copper-scandium intermediate alloy ingot. Through detection, the alloy comprises the following components in percentage by mass: 80% of copper and 20% of scandium.
Embodiment 3 preparation method of copper-scandium master alloy
500g of fused salt is put into a graphite crucible with the diameter of 80mm, wherein the fused salt electrolyte system is 5 parts of ScF according to the mass percentage370 parts of LiF and 55 parts of MgCl; a molybdenum crucible which is insulated from graphite and has a diameter of 50mm is placed at the center of the bottom of the graphite crucible to serve as a holding crucible; then, the graphite crucible is put into a furnace and heated to 1000 ℃, after the molten salt is melted, a copper rod with the diameter of 20mm is inserted into the molten salt, and the immersion depth is 30 mm; electrolyzing with graphite crucible as anode and copper rod as cathode at current density of 0.5A/cm2(ii) a And (4) taking out the molybdenum crucible by using crucible tongs after 2h of electrolysis, and casting the collected copper-scandium intermediate alloy liquid into a mould to prepare a copper-scandium intermediate alloy ingot. Through detection, the alloy comprises the following components in percentage by mass: 90% of copper and 10% of scandium.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (4)

1. A preparation method of a copper-scandium intermediate alloy is characterized by comprising the following steps: in a molten salt electrolyte containing scandium, a copper metal electrode is used as a consumable cathode, graphite is used as an anode, and a copper-scandium intermediate alloy is prepared through molten salt electrolysis; the molten salt electrolyte comprises the following components in parts by weight: 20-70 parts of LiF and 5-60 parts of ScF30-55 parts of MCl or/and MF, wherein M is one or more of alkali metal elements and alkaline earth metal elements; the temperature of the molten salt electrolysis is 875 ℃, and the cathode current density of the molten salt electrolysis is 40A/cm2Preparing a copper-scandium master alloy with a scandium content of 75%; or: the temperature of the molten salt electrolysis is 1100 ℃, and the current density of the cathode of the molten salt electrolysis is 10A/cm2Preparing a copper-scandium master alloy with a scandium content of 20%; or: the temperature of the molten salt electrolysis is 1000 ℃, and the cathode current density of the molten salt electrolysis is 0.5A/cm2And preparing the copper-scandium master alloy with the scandium content material of 10 percent.
2. The method of claim 1, wherein: adding a raw material Sc to the molten salt electrolyte2O3，Sc2O3The mass of the added salt is 0-30% of the mass of the fused salt.
3. The method of claim 1, wherein: and a holding crucible is arranged below the copper cathode and used for collecting a copper-scandium intermediate alloy product, and the holding crucible is a molybdenum crucible, a tungsten crucible, a tantalum crucible or a graphite crucible.
4. Use of a copper-scandium master alloy produced according to any one of claims 1 to 3 for producing scandium-containing alloys of other metals.
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