CN116397269A - Preparation method of magnesium-lithium-rare earth alloy based on fused salt codeposition - Google Patents
Preparation method of magnesium-lithium-rare earth alloy based on fused salt codeposition Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 44
- 239000000956 alloy Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003839 salts Chemical class 0.000 title claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 120
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 66
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 39
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000001103 potassium chloride Substances 0.000 claims abstract description 19
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 19
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 18
- -1 rare earth chloride Chemical class 0.000 claims abstract description 17
- 239000007921 spray Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229960002337 magnesium chloride Drugs 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229940091250 magnesium supplement Drugs 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 229910000733 Li alloy Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000001989 lithium alloy Substances 0.000 description 5
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 4
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910000858 La alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- WPRLHGDKCHANPM-UHFFFAOYSA-M O.O.O.O.O.[Cl-].[Li+] Chemical compound O.O.O.O.O.[Cl-].[Li+] WPRLHGDKCHANPM-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- SQKWGPOIVHMUNF-UHFFFAOYSA-K cerium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3] SQKWGPOIVHMUNF-UHFFFAOYSA-K 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 description 1
- GPSWHHINFSGBSI-UHFFFAOYSA-M lithium;chloride;trihydrate Chemical compound [Li+].O.O.O.[Cl-] GPSWHHINFSGBSI-UHFFFAOYSA-M 0.000 description 1
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- XEEYVTMVFJEEEY-UHFFFAOYSA-L magnesium;dichloride;tetrahydrate Chemical compound O.O.O.O.[Mg+2].[Cl-].[Cl-] XEEYVTMVFJEEEY-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a preparation method of a magnesium-lithium-rare earth alloy based on fused salt codeposition, which comprises the following steps: mixing anhydrous lithium chloride, potassium chloride and calcium fluoride with each other to form a first mixed material and heating to form a molten electrolyte; mixing the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride with each other to form a second mixed material, and heating the second mixed material to form a molten electrolytic raw material; placing molten electrolyte in electrolysis equipment, carrying out direct current electrolysis process by taking a molybdenum rod or a tungsten rod as a cathode and graphite as an anode, and gradually and continuously adding molten electrolysis raw materials into the molten electrolyte in a spray droplet mode in the direct current electrolysis process for electrolysis; collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. The technical scheme of the invention uses the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride as the electrolytic raw materials and combines a specific charging mode to prepare the magnesium-lithium-rare earth alloy, thereby reducing the difficulty and the production cost of the production process.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a preparation method of a magnesium-lithium-rare earth alloy based on fused salt codeposition.
Background
The magnesium-lithium alloy has excellent comprehensive properties, namely high specific strength, high specific rigidity, good heat conductivity, excellent electromagnetic shielding and damping properties and the like, and has wide application prospects in the fields of aerospace, weaponry, electronic information, automobile industry and the like. Although magnesium-lithium alloys have good plasticity, the binary alloys have lower strength and usually require the addition of other alloying elements for further alloying to form ternary or multi-element alloys to obtain high strength alloys. Because rare earth elements (RE) have unique extra-nuclear electron arrangement, the alloy liquid is purified, the mechanical property of the alloy is improved, the corrosion resistance is enhanced, and the like, after RE is added into the magnesium-lithium alloy, the alloy has the effects of refining particle size, changing microstructure, and the like, thereby enhancing the strength, the hardness, the heat resistance, the corrosion resistance, and the like of the alloy. In addition, RE can be added to raise the recrystallization temperature of magnesium-lithium alloy, and this can raise the effect of ageing strengthening, and RE can also purify magnesium-lithium alloy melt, raise its casting performance and raise its comprehensive mechanical performance.
Chinese patent application CN101302594A reports a preparation method of magnesium-lithium-persimmon lanthanum alloy, which uses MgCl 2 And (3) taking +LiCl +KCl +KF as an electrolyte system, adding cerium carbonate and lanthanum carbonate, and then preparing the magnesium lithium-persimmon lanthanum alloy by a fusion electrolysis method. In the preparation process, the electrolysis raw materials are all anhydrous materials for electrolysis, namely MgCl in an electrolyte system 2 Both LiCl, KCl, KF require a dehydration treatment. Among them, the process of dehydrating hydrous magnesium chloride to anhydrous magnesium chloride is particularly difficult, and in particular: although most of the crystal water can be easily removed by heating magnesium chloride hexahydrate, the later 1-2 pieces of crystal water are difficult to remove, and anhydrous magnesium chloride can be obtained only by dehydration under the protection of chlorine gas or hydrogen chloride gas, or magnesium chloride is hydrolyzed to produce magnesium oxide and other impurities harmful to electrolysis. Therefore, the anhydrous magnesium chloride is adopted as the electrolysis raw material in the prior art, so that the process difficulty is increased, the energy consumption is increased, and the production cost is high.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a magnesium-lithium-rare earth alloy based on fused salt codeposition, so as to reduce the preparation process difficulty and the production cost of the magnesium-lithium-rare earth alloy.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing a magnesium-lithium-rare earth alloy based on molten salt co-deposition, comprising:
mixing anhydrous lithium chloride, potassium chloride and calcium fluoride with each other to form a first mixed material, and heating the first mixed material to form a molten electrolyte;
mixing hydrous magnesium chloride, hydrous rare earth chloride and hydrous lithium chloride with each other to form a second mixed material, and heating the second mixed material to form a molten electrolytic raw material;
placing the molten electrolyte in electrolysis equipment, carrying out direct current electrolysis process by taking a molybdenum rod or a tungsten rod as a cathode and graphite as an anode, and gradually and continuously adding the molten electrolysis raw material into the molten electrolyte in a spray droplet mode in the direct current electrolysis process for electrolysis;
collecting and obtaining the co-deposited magnesium-lithium-rare earth alloy on the cathode after the electrolysis is completed.
In the preferred scheme, in the first mixed material, the mass percent of lithium chloride is 48% -50%, the mass percent of potassium chloride is 48% -50%, and the mass percent of calcium fluoride is 2% -4%.
In a preferred embodiment, the heating temperature for heating the first mixture to form a molten electrolyte is 600 ℃ to 800 ℃.
In a preferred embodiment, the first mixture is first added to the electrolysis apparatus, and then the first mixture is heated in the electrolysis apparatus to form a molten electrolyte.
In a preferred scheme, in the second mixed material, the mass ratio of the hydrous magnesium chloride to the hydrous rare earth chloride to the hydrous lithium chloride is (1-6): (1-4): (1-4).
In a preferred embodiment, the heating temperature for heating the second mixture to form a molten electrolytic raw material is 130 to 180 ℃.
In the preferred scheme, the second mixed material is firstly placed in a muffle furnace to be heated to form the molten electrolysis raw material, and then the molten electrolysis raw material is gradually and continuously added into the molten electrolyte in a spray droplet mode through a heat preservation spray nozzle in the direct current electrolysis process to carry out electrolysis.
In a preferred embodiment, the aqueous magnesium chloride contains 0.5 to 6 crystal waters, the aqueous rare earth chloride contains 0.5 to 7 crystal waters, and the aqueous lithium chloride contains 0.5 to 5 crystal waters.
In a preferred embodiment, the aqueous rare earth chloride is aqueous lanthanum chloride or aqueous cerium chloride.
In a preferred embodiment, the direct current electrolysis process is carried out under the following process conditions: the electrolysis current is 4000A-10000A, the electrolysis voltage is 5V-15V, the electrolysis temperature is 600-800 ℃, and the electrolysis time is 1-4 h.
According to the preparation method of the magnesium-lithium-rare earth alloy, the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride are used as the electrolysis raw materials, the electrolysis raw materials are heated and melted firstly and gradually and continuously added into a molten electrolyte system in a spray droplet mode for electrolysis, and therefore the magnesium-lithium-rare earth alloy with uniform dispersion and good performance can be prepared. In the method, the electrolytic raw materials such as the hydrous magnesium chloride do not need to be dehydrated in advance, so that the difficulty is reduced, and the production energy consumption and the production cost are also reduced.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application so that others skilled in the art will be able to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The embodiment of the invention provides a preparation method of a magnesium-lithium-rare earth alloy based on fused salt codeposition, which comprises the following steps:
and S1, mixing anhydrous lithium chloride, potassium chloride and calcium fluoride with each other to form a first mixed material, and heating the first mixed material to form a molten electrolyte.
In the preferred scheme, in the first mixed material, the mass percent of lithium chloride is 48% -50%, the mass percent of potassium chloride is 48% -50%, and the mass percent of calcium fluoride is 2% -4%. By adding a small amount of calcium fluoride into the electrolyte system, the oxidation of the liquid magnesium alloy can be prevented, the stable electrolysis can be kept, and the current efficiency can be improved.
In a preferred embodiment, the heating temperature for heating the first mixture to form a molten electrolyte is 600 to 800 ℃.
In a preferred embodiment, the first mixture is first introduced into an electrolysis apparatus, and then the first mixture is heated in the electrolysis apparatus to form a molten electrolyte.
And S2, mixing the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride to form a second mixed material, and heating the second mixed material to form a molten electrolytic raw material.
In a preferred scheme, in the second mixed material, the mass ratio of the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride is (1-6): (1-4): (1-4).
In a preferred embodiment, the heating temperature for heating the second mixture to form a molten electrolytic raw material is 130 to 180 ℃. Preferably, the second mixture is heated in a muffle furnace to form the molten electrolytic raw material.
And S3, placing the molten electrolyte into electrolysis equipment, carrying out a direct current electrolysis process by taking a molybdenum rod or a tungsten rod as a cathode and graphite as an anode, and gradually and continuously adding the molten electrolysis raw material into the molten electrolyte in a spray droplet mode in the direct current electrolysis process for electrolysis.
By adopting a preheating and melting electrolysis raw material and continuous drip-shaped feeding mode, the molten salt electrolyte can be prevented from splashing in the feeding process, the stable electrolysis is ensured, and the method has positive effects of improving the quality, the yield and the yield of products, improving the current efficiency and the like. In a preferred scheme, the molten electrolysis raw material is gradually and continuously added into the molten electrolyte in a spray droplet mode through a heat-preserving spray nozzle in the direct current electrolysis process for electrolysis.
In a preferred embodiment, the direct current electrolysis process is carried out under the following process conditions: the electrolysis current is 4000A-10000A, the electrolysis voltage is 5V-15V, the electrolysis temperature is 600-800 ℃, and the electrolysis time is 1-4 h.
And S4, collecting and obtaining the co-deposited magnesium-lithium-rare earth alloy on the cathode after the electrolysis is completed.
Wherein, in the embodiment described above, the hydrous magnesium chloride may be selected to contain 0.5 to 6 crystal water hydrous magnesium chloride, the hydrous rare earth chloride may be selected to contain 0.5 to 7 crystal water hydrous rare earth chloride, and the hydrous lithium chloride may be selected to contain 0.5 to 5 crystal water hydrous lithium chloride. Further, the aqueous rare earth chloride is preferably aqueous lanthanum chloride or aqueous cerium chloride.
Example 1
Anhydrous lithium chloride, potassium chloride and calcium fluoride are mixed with each other and added to an electrolytic cell, and heated at a temperature of 650 ℃ to form a molten electrolyte. Wherein the mass percentage of lithium chloride is 49%, the mass percentage of potassium chloride is 49%, and the mass percentage of calcium fluoride is 2%.
Crushing and mixing magnesium chloride hexahydrate, lanthanum chloride heptahydrate and lithium chloride monohydrate in a mass ratio of 4:4:2, and heating in a muffle furnace at 150 ℃ to form a molten electrolysis raw material.
In the electrolytic bath, a metal tungsten rod is used as a cathode, a graphite crucible is used as an anode for electrolysis, and in the electrolysis process, molten electrolysis raw materials in a muffle furnace are sprayed into high-temperature electrolyte through a heat preservation spray nozzle.
The specific technological parameters of electrolysis are as follows: the electrolysis current is 4000A, the electrolysis voltage is 12.0V, the electrolysis temperature is 650 ℃, and the electrolysis time is 1h.
Collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. Through tests, the mass fractions of magnesium, lanthanum and lithium in the alloy obtained by the implementation are 58%, 26% and 22%, respectively.
The comprehensive mechanical properties of the alloy are as follows: the density is 1.38g/cm3, the tensile strength is 240MPa, the yield strength is 150MPa, the elongation is 11%, and the elastic modulus is 48GPa.
Example 2
Anhydrous lithium chloride, potassium chloride and calcium fluoride are mixed with each other and added to an electrolytic cell, and heated at 700 ℃ to form a molten electrolyte. Wherein the mass percentage of lithium chloride is 49%, the mass percentage of potassium chloride is 49%, and the mass percentage of calcium fluoride is 2%.
And (3) crushing and mixing magnesium chloride hexahydrate, cerium chloride heptahydrate and lithium chloride monohydrate in a mass ratio of 1:4:4, and heating in a muffle furnace at 160 ℃ to form a molten electrolysis raw material.
In the electrolytic bath, a metal molybdenum rod is used as a cathode, a graphite crucible is used as an anode for electrolysis, and in the electrolysis process, molten electrolysis raw materials in a muffle furnace are sprayed into high-temperature electrolyte through a heat preservation spray nozzle.
The specific technological parameters of electrolysis are as follows: the electrolysis current is 5000A, the electrolysis voltage is 5V, the electrolysis temperature is 700 ℃, and the electrolysis time is 4h.
Collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. Through tests, the mass fractions of magnesium, cerium and lithium in the alloy obtained by the implementation are 22%, 45% and 43%, respectively.
The comprehensive mechanical properties of the alloy are as follows: the density is 1.32g/cm3, the tensile strength is 210MPa, the yield strength is 130MPa, the elongation is 15%, and the elastic modulus is 45GPa.
Example 3
Anhydrous lithium chloride, potassium chloride and calcium fluoride are mixed with each other and added to an electrolytic cell, and heated at a temperature of 750 ℃ to form a molten electrolyte. Wherein the mass percentage of lithium chloride is 49%, the mass percentage of potassium chloride is 49%, and the mass percentage of calcium fluoride is 2%.
Crushing and mixing magnesium chloride tetrahydrate, lanthanum chloride hexahydrate and lithium chloride pentahydrate with the mass ratio of 5:4:1, and heating in a muffle furnace at 130 ℃ to form a molten electrolysis raw material.
In the electrolytic bath, a metal tungsten rod is used as a cathode, a graphite crucible is used as an anode for electrolysis, and in the electrolysis process, molten electrolysis raw materials in a muffle furnace are sprayed into high-temperature electrolyte through a heat preservation spray nozzle.
The specific technological parameters of electrolysis are as follows: the electrolysis current is 10000A, the electrolysis voltage is 15.0V, the electrolysis temperature is 750 ℃, and the electrolysis time is 2h.
Collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. Through tests, the mass fractions of magnesium, lanthanum and lithium in the alloy obtained by the implementation are 72%, 18% and 10% respectively.
The comprehensive mechanical properties of the alloy are as follows: the density is 1.68g/cm3, the tensile strength is 240MPa, the yield strength is 180MPa, the elongation is 10%, and the elastic modulus is 55GPa.
Example 4
Anhydrous lithium chloride, potassium chloride and calcium fluoride are mixed with each other and added to an electrolytic cell, and heated at 680 ℃ to form a molten electrolyte. Wherein the mass percentage of lithium chloride is 49%, the mass percentage of potassium chloride is 49%, and the mass percentage of calcium fluoride is 2%.
And (3) crushing and mixing magnesium chloride hexahydrate, cerium chloride hexahydrate and lithium chloride monohydrate in a mass ratio of 5:1:4, and heating in a muffle furnace at 180 ℃ to form a molten electrolysis raw material.
In the electrolytic bath, a metal tungsten rod is used as a cathode, a graphite crucible is used as an anode for electrolysis, and in the electrolysis process, molten electrolysis raw materials in a muffle furnace are sprayed into high-temperature electrolyte through a heat preservation spray nozzle.
The specific technological parameters of electrolysis are as follows: the electrolysis current is 6000A, the electrolysis voltage is 6.5V, the electrolysis temperature is 680 ℃, and the electrolysis time is 2h.
Collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. Through tests, the mass fractions of magnesium, cerium and lithium in the alloy obtained by the implementation are 55%, 11% and 44%, respectively.
The comprehensive mechanical properties of the alloy are as follows: the density is 1.66g/cm3, the tensile strength is 260MPa, the yield strength is 190MPa, the elongation is 7%, and the elastic modulus is 60GPa.
Example 5
Anhydrous lithium chloride, potassium chloride and calcium fluoride are mixed with each other and added to an electrolytic cell, and heated at 800 ℃ to form a molten electrolyte. Wherein the mass percentage of lithium chloride is 49%, the mass percentage of potassium chloride is 49%, and the mass percentage of calcium fluoride is 2%.
And (3) crushing and mixing the magnesium chloride dihydrate, the lanthanum chloride heptahydrate and the lithium chloride trihydrate with the mass ratio of 6:1.5:2.5, and heating in a muffle furnace at 130 ℃ to form a molten electrolysis raw material.
In the electrolytic bath, a metal tungsten rod is used as a cathode, a graphite crucible is used as an anode for electrolysis, and in the electrolysis process, molten electrolysis raw materials in a muffle furnace are sprayed into high-temperature electrolyte through a heat preservation spray nozzle.
The specific technological parameters of electrolysis are as follows: the electrolysis current is 4000A, the electrolysis voltage is 8V, the electrolysis temperature is 800 ℃, and the electrolysis time is 4h.
Collecting the magnesium-lithium-rare earth alloy on a cathode after the electrolysis is completed to obtain the co-deposited magnesium-lithium-rare earth alloy. Through tests, the mass fractions of magnesium, lanthanum and lithium in the alloy obtained by the implementation are 75%, 16% and 19%, respectively.
The comprehensive mechanical properties of the alloy are as follows: the density is 1.72g/cm3, the tensile strength is 240MPa, the yield strength is 170MPa, the elongation is 8%, and the elastic modulus is 58GPa.
In summary, according to the preparation method of the magnesium-lithium-rare earth alloy provided in the above embodiment, the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride are used as the electrolysis raw materials, and the electrolysis raw materials are heated and melted first and are gradually and continuously added into the molten electrolyte system in a spray droplet manner for electrolysis, so that the magnesium-lithium-rare earth alloy with uniform dispersion and good performance can be prepared. In the method, the pre-dehydration treatment of the electrolytic raw materials such as the hydrous magnesium chloride is avoided, so that the difficulty is reduced, and the production energy consumption and the production cost are also reduced.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will appreciate that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A method for preparing a magnesium-lithium-rare earth alloy based on molten salt co-deposition, which is characterized by comprising the following steps:
mixing anhydrous lithium chloride, potassium chloride and calcium fluoride with each other to form a first mixed material, and heating the first mixed material to form a molten electrolyte;
mixing hydrous magnesium chloride, hydrous rare earth chloride and hydrous lithium chloride with each other to form a second mixed material, and heating the second mixed material to form a molten electrolytic raw material;
placing the molten electrolyte in electrolysis equipment, carrying out direct current electrolysis process by taking a molybdenum rod or a tungsten rod as a cathode and graphite as an anode, and gradually and continuously adding the molten electrolysis raw material into the molten electrolyte in a spray droplet mode in the direct current electrolysis process for electrolysis;
collecting and obtaining the co-deposited magnesium-lithium-rare earth alloy on the cathode after the electrolysis is completed.
2. The preparation method according to claim 1, wherein in the first mixed material, the mass percentage of lithium chloride is 48% -50%, the mass percentage of potassium chloride is 48% -50%, and the mass percentage of calcium fluoride is 2% -4%.
3. The method of claim 1 or 2, wherein the heating temperature for heating the first mixture to form the molten electrolyte is 600 ℃ to 800 ℃.
4. A method of preparing according to claim 3, wherein the first mixed material is first added to the electrolysis apparatus and then heated in the electrolysis apparatus to form a molten electrolyte.
5. The preparation method according to claim 1, wherein the mass ratio of the aqueous magnesium chloride, the aqueous rare earth chloride and the aqueous lithium chloride in the second mixed material is (1 to 6): (1-4): (1-4).
6. The method according to claim 5, wherein the heating temperature for heating the second mixed material to form the molten electrolytic raw material is 130 ℃ to 180 ℃.
7. The method according to claim 6, wherein the second mixture is heated in a muffle furnace to form the molten electrolysis raw material, and then the molten electrolysis raw material is continuously added into the molten electrolyte step by step in a spray droplet manner through a heat-insulating spray nozzle in the direct-current electrolysis process for electrolysis.
8. The production method according to any one of claims 1 or 5 to 7, wherein the aqueous magnesium chloride contains 0.5 to 6 crystal waters, the aqueous rare earth chloride contains 0.5 to 7 crystal waters, and the aqueous lithium chloride contains 0.5 to 5 crystal waters.
9. The method according to claim 8, wherein the aqueous rare earth chloride is aqueous lanthanum chloride or aqueous cerium chloride.
10. The method according to claim 1, wherein the direct current electrolysis process is carried out under the following process conditions: the electrolysis current is 4000A-10000A, the electrolysis voltage is 5V-15V, the electrolysis temperature is 600-800 ℃, and the electrolysis time is 1-4 h.
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