CN115852183B - Smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing - Google Patents
Smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910000946 Y alloy Inorganic materials 0.000 title claims abstract description 26
- 238000003723 Smelting Methods 0.000 title claims abstract description 20
- 238000010146 3D printing Methods 0.000 title claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 128
- 230000004907 flux Effects 0.000 claims abstract description 77
- 238000007664 blowing Methods 0.000 claims abstract description 75
- 239000011777 magnesium Substances 0.000 claims abstract description 71
- 239000000155 melt Substances 0.000 claims abstract description 61
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011261 inert gas Substances 0.000 claims abstract description 49
- 229910018137 Al-Zn Inorganic materials 0.000 claims abstract description 45
- 229910018573 Al—Zn Inorganic materials 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 239000011701 zinc Substances 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005266 casting Methods 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 22
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 56
- 239000000956 alloy Substances 0.000 claims description 56
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 48
- 229910000733 Li alloy Inorganic materials 0.000 claims description 47
- 239000001989 lithium alloy Substances 0.000 claims description 47
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 26
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 24
- 239000007921 spray Substances 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 66
- 229910052786 argon Inorganic materials 0.000 description 33
- 239000007789 gas Substances 0.000 description 29
- MIOQWPPQVGUZFD-UHFFFAOYSA-N magnesium yttrium Chemical compound [Mg].[Y] MIOQWPPQVGUZFD-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012535 impurity Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052729 chemical element Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005242 forging Methods 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing, which comprises the following steps: according to the composition of the Mg-Li-Al-Zn-Y alloy, firstly melting a magnesium source, adding an aluminum source and a zinc source into the obtained magnesium melt to melt, and obtaining the Mg-Al-Zn melt; carrying out primary inert gas rotary blowing refining on the Mg-Al-Zn melt at the temperature of 720-750 ℃ to obtain purified Mg-Al-Zn melt; adding yttrium source into the purified Mg-Al-Zn melt for melting to obtain Mg-Al-Zn-Y melt; performing secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain purified Mg-Al-Zn-Y melt; adding a lithium source into the purified Mg-Al-Zn-Y melt for melting to obtain a Mg-Al-Zn-Y-Li melt; and when the temperature of the melt is 660-720 ℃, adopting a refining flux to refine the Mg-Al-Zn-Y-Li melt by a tertiary flux. The method provided by the invention sequentially carries out primary inert gas rotary blowing refining purification, secondary inert gas rotary blowing refining and tertiary flux refining, reduces the slag content in the melt and ensures the purity of the melt before casting.
Description
Technical Field
The invention relates to the technical field of metal metallurgy, in particular to a smelting purification method of Mg-Li-Al-Zn-Y alloy melt for three-dimensional printing.
Background
The modern industry has more and more obvious requirements for ultra-light high-strength materials, and the magnesium-lithium alloy has remarkable advantages and is closely focused by scientists, such as low density (generally 1.25-1.65g/cm 3, which is 1/3-1/2 lighter than common magnesium alloy and 1/2 of aluminum alloy), high specific strength, high specific rigidity, good electromagnetic shielding performance and damping property and excellent cutting machining performance. Therefore, the magnesium-lithium alloy is widely applied to the fields of aerospace, automobiles and electronic products, and has very broad market prospect.
At present, space components with complex structures and large sizes are mainly produced by adopting a casting method, if the magnesium-lithium alloy is promoted to be applied to the space components, magnesium-lithium alloy blanks are generally manufactured by adopting casting, forging and other methods, and then a plurality of working procedures such as subsequent machining and the like are carried out, so that reserved machining allowance is larger, the utilization rate of raw materials is very low, the stock preparation period is long, and the development progress of models is severely restricted. The additive manufacturing technology (three-dimensional printing) has the advantages of no need of a die, short manufacturing period, low cost and the like, can provide more design ideas for manufacturing complex aerospace components, and is beneficial to realizing rapid and effective cooperation of design, process and manufacturing.
The three-dimensional printing technology firstly needs to have high-quality magnesium-lithium alloy cast ingots. When the magnesium-lithium alloy is smelted and cast in the atmosphere, magnesium and lithium in the alloy are easy to react with substances such as air, oxygen and water in smelting equipment or raw materials, oxidation and even combustion loss of alloy elements are caused, and impurities such as oxides and carbides of the magnesium-lithium elements can be introduced to pollute the melt. Meanwhile, the raw material of the magnesium-lithium alloy also contains a certain amount of inclusions. These impurities significantly reduce the mechanical and corrosion resistance properties of the magnesium-lithium alloy. Therefore, the melt is subjected to refining and purifying treatment in the smelting process of the magnesium-lithium alloy so as to remove impurities in the melt and prevent the impurities from affecting the quality of the cast ingot. The currently studied refining process of the magnesium-lithium alloy mainly comprises flux refining, and the used refining flux mainly comprises lithium chloride and lithium fluoride series flux (such as Yao Xinzhao, research on casting process and tissue property of the magnesium-lithium alloy [ M ], university of Hunan, 2006, shuoshi treatises, P1-32.), but the flux is inconvenient to separate from the melt in the refining process, and is easy to form flux inclusion, so that the pollution to the melt is increased, and the quality of cast ingots is influenced; if a common magnesium alloy flux (such as Liu Wanghan Bo, et al, research progress of magnesium alloy melt purification technology [ J ], casting, 2015,64 (6) P521-527.) is adopted, lithium reacts with magnesium chloride which is a main component in the flux to consume lithium element in the melt, so that the components of the cast ingot are unstable.
Disclosure of Invention
In view of the above, the invention aims to provide a smelting and purifying method for Mg-Li-Al-Zn-Y alloy for three-dimensional printing, which reduces the slag content of the Mg-Li-Al-Zn-Y alloy and ensures the purity of cast ingots.
The invention provides a smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing, which comprises the following steps:
According to the composition of the Mg-Li-Al-Zn-Y alloy, firstly melting a magnesium source, adding an aluminum source and a zinc source at 680-700 ℃ into the magnesium melt for melting to obtain a Mg-Al-Zn melt;
carrying out primary inert gas rotary blowing refining on the Mg-Al-Zn melt at the temperature of 720-750 ℃ to obtain purified Mg-Al-Zn melt;
adding yttrium source into the purified Mg-Al-Zn melt to melt at the temperature of 730-760 ℃ to obtain Mg-Al-Zn-Y melt;
Performing secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain purified Mg-Al-Zn-Y melt;
Adding a lithium source into the purified Mg-Al-Zn-Y melt for melting to obtain a Mg-Al-Zn-Y-Li melt;
And when the temperature of the melt is 660-720 ℃, adopting a refining flux to refine the Mg-Al-Zn-Y-Li melt by a tertiary flux.
Preferably, the conditions of the primary inert gas rotary blowing refining include: the rotating speed of the spray head is 100-200 r/min, the flow rate of the inert gas is 1-3L/min, and the spraying time is 4-10 min.
Preferably, the conditions of the secondary inert gas rotary blowing refining include: the rotating speed of the spray head is 100-200 r/min, the flow rate of the inert gas is 1-3L/min, and the spraying time is 8-15 min.
Preferably, the refining flux comprises the following components in percentage by mass: 35-55% of potassium bromide, 10-35% of calcium chloride, 5-20% of lithium chloride, 5-15% of lithium fluoride, 1-10% of yttrium chloride and 2-15% of carbonate foaming agent.
Preferably, the addition amount of the refining flux is 1-6% of the mass of the Mg-Al-Zn-Y-Li melt.
Preferably, the carbonate foaming agent is one or more of lithium carbonate, calcium carbonate and potassium carbonate.
Preferably, the Mg-Li-Al-Zn-Y alloy comprises the following element compositions in percentage by mass: 6 to 14 percent of Li, 1 to 5 percent of Al, 1 to 5 percent of Zn, 0.2 to 1.5 percent of Y and the balance of Mg.
Preferably, the three-stage flux refining time is 5-10 min, and the heat preservation temperature is 660-720 ℃.
Preferably, the temperature of the purified Mg-Al-Zn-Y melt is 660-720 ℃ when the lithium source is added.
Preferably, the magnesium source, the aluminum source, the zinc source and the yttrium source are preheated before being melted, and the preheating temperature is 180-200 ℃.
The invention provides a smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing, which comprises the following steps: according to the composition of the Mg-Li-Al-Zn-Y alloy, firstly melting a magnesium source, adding an aluminum source and a zinc source at 680-700 ℃ into the magnesium melt for melting to obtain a Mg-Al-Zn melt; carrying out primary inert gas rotary blowing refining on the Mg-Al-Zn melt at the temperature of 720-750 ℃ to obtain purified Mg-Al-Zn melt; adding yttrium source into the purified Mg-Al-Zn melt to melt at the temperature of 730-760 ℃ to obtain Mg-Al-Zn-Y melt; performing secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain purified Mg-Al-Zn-Y melt; adding a lithium source into the purified Mg-Al-Zn-Y melt for melting to obtain a Mg-Al-Zn-Y-Li melt; and when the temperature of the melt is 660-720 ℃, adopting a refining flux to refine the Mg-Al-Zn-Y-Li melt by a tertiary flux. In the smelting process of main elements Mg, al and Zn of the magnesium-lithium alloy, the temperature of the melt is about 720-750 ℃ before adding the element Y, at this time, partial inclusion is easy to remove, primary inert gas rotary blowing refining purification is carried out at the temperature, and the slag content in the melt is reduced for the first time; after the primary refining is finished, adding yttrium source, keeping the temperature for a long time, and forming new inclusion, so that the secondary inert gas rotary blowing refining is carried out before adding active element Li at 680-720 ℃ to further improve the purity of the melt and reduce the slag content; after Li element is added, the melt is in a very easily oxidized state, and three-stage flux refining is performed at the moment, so that the slag content in the melt is further reduced, and the purity of the melt before casting is ensured.
Further, in the three-stage flux refining, the refining flux comprises the following components in percentage by mass: 35-55% of potassium bromide, 10-35% of calcium chloride, 5-20% of lithium chloride, 5-15% of lithium fluoride, 1-10% of yttrium chloride and 2-15% of carbonate foaming agent. The refining flux can reduce the Li burning loss rate and the Y sedimentation rate, does not react with lithium element in the use process, can reduce the loss of lithium, and ensures the yield of the lithium element; the refining flux also has an adsorption effect, wherein the carbonate foaming agent is heated and decomposed to continuously release tiny inert gas bubbles, nonmetallic inclusion can be adsorbed in the process of floating up the bubbles, so that the nonmetallic inclusion is agglomerated into large particles, the removal rate of various inclusion is greatly improved, the refining effect is stable, and the slag is easily separated from alloy liquid and conveniently removed.
The refining flux used in the invention has better melting point, density and wettability, has the functions of the refining agent and the covering agent, can effectively isolate air when being used as the covering agent, provides sufficient protection for the melt, and meanwhile, the released protective gas dilutes harmful gases such as hydrogen chloride, thereby remarkably reducing the emission of the harmful gases in the smelting process and achieving the purpose of no public hazard; when being used as a refining agent, the refining agent can be fully contacted with impurities in the melt to remove the impurities, so as to ensure the refining effect; the refining flux can reduce the dosage of the flux.
The magnesium-lithium alloy obtained by the method provided by the invention has the advantages that the slag content is greatly reduced, the burning loss rate of Li element is reduced, the sedimentation rate of Y element is reduced, the mechanical property is improved, and the technical support is provided for the development and three-dimensional printing application of high-quality magnesium-lithium alloy; and the smelting cost is reduced.
Detailed Description
The invention provides a smelting and purifying method of Mg-Li-Al-Zn-Y alloy for three-dimensional printing, which comprises the following steps:
According to the composition of the Mg-Li-Al-Zn-Y alloy, firstly melting a magnesium source, adding an aluminum source and a zinc source at 680-700 ℃ into the magnesium melt for melting to obtain a Mg-Al-Zn melt;
carrying out primary inert gas rotary blowing refining on the Mg-Al-Zn melt at the temperature of 720-750 ℃ to obtain purified Mg-Al-Zn melt;
adding yttrium source into the purified Mg-Al-Zn melt to melt at the temperature of 730-760 ℃ to obtain Mg-Al-Zn-Y melt;
Performing secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain purified Mg-Al-Zn-Y melt;
Adding a lithium source into the purified Mg-Al-Zn-Y melt for melting to obtain a Mg-Al-Zn-Y-Li melt;
And when the temperature of the melt is 660-720 ℃, adopting a refining flux to refine the Mg-Al-Zn-Y-Li melt by a tertiary flux.
The temperature of the melt is about 720-750 ℃ before the Y source is added, at this time, partial inclusion is easy to clear, primary inert gas rotary blowing refining is carried out at the temperature, and the slag content in the melt is reduced for the first time; after the primary inert gas rotary blowing refining is finished, yttrium source is added, the heat preservation time is longer, further oxidation phenomenon is generated, and new inclusion is formed, so that the secondary inert gas rotary blowing refining is carried out before the active element Li is added at the temperature ranging from 680 ℃ to 720 ℃ to further improve the purity of the melt and reduce the slag content. After Li element is added at 660-720 ℃, the melt is in a state of being very easy to oxidize, and three-stage flux refining is performed at the moment, so that the Li burning loss rate and the Y sedimentation rate are reduced, the slag content in the melt can be further reduced, and the purity of the melt before casting is ensured.
According to the composition of Mg-Li-Al-Zn-Y alloy, a magnesium source is melted to obtain a magnesium melt. The method for melting the magnesium source is not particularly limited, and a method for melting the magnesium source, which is well known to those skilled in the art, may be employed.
After the magnesium source is melted, when the temperature of the magnesium melt is 680-700 ℃, an aluminum source and a zinc source are added into the magnesium melt to melt, so that the Mg-Al-Zn melt is obtained. In the present invention, the temperature of the magnesium melt may be in particular 680, 690 or 700 ℃. In the embodiment of the invention, the Mg-Li-Al-Zn-Y alloy preferably comprises the following element compositions in percentage by mass: 6 to 14 percent of Li, 1 to 5 percent of Al, 1 to 5 percent of Zn, 0.2 to 1.5 percent of Y and the balance of Mg.
In the present invention, the Mg-Li-Al-Zn-Y alloy preferably includes 6 to 14wt% Li, and in particular embodiments may be 6, 7, 8, 9, 10, 11, 12, 13, or 14wt%.
In the present invention, the Mg-Li-Al-Zn-Y alloy preferably includes Al 1 to 5wt%, and in particular embodiments may be 1,2,3,4, or 5wt%.
In the present invention, the Mg-Li-Al-Zn-Y alloy preferably includes Zn in an amount of 1 to 5wt%, and in specific embodiments may be 1,2,3,4, or 5wt%.
In the present invention, the Mg-Li-Al-Zn-Y alloy preferably includes 0.2 to 1.5wt% Y, and in particular embodiments may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5wt%.
In the present invention, the Mg-Li-Al-Zn-Y alloy preferably includes the balance Mg.
The kinds of the magnesium source, the aluminum source and the zinc source are not particularly limited, and those known to those skilled in the art may be used. In an embodiment of the present invention, the magnesium source may be pure magnesium, the aluminum source may be pure aluminum, and the zinc source may be pure zinc.
In the present invention, the magnesium, aluminum and zinc sources are preferably preheated prior to melting, the preheating preferably being at a temperature of 180 to 200 ℃, and in particular embodiments may be 180, 190 or 200 ℃.
The melting method is not particularly limited, and the technical scheme of melting the magnesium-lithium alloy, which is well known to those skilled in the art, can be adopted.
After the Mg-Al-Zn melt is obtained, the invention carries out primary inert gas rotary blowing refining on the Mg-Al-Zn melt when the temperature of the melt is 720-750 ℃ to obtain the purified Mg-Al-Zn melt. In the embodiment of the invention, the primary inert gas rotary blowing refining is performed by inert gas rotary blowing equipment, and the type of the inert gas rotary blowing equipment is not particularly limited. In the present invention, the inert gas is preferably argon or helium. In the invention, the rotating speed of the spray head is preferably 100-200 r/min during the primary inert gas rotary blowing refining, and can be specifically 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200r/min in the embodiment; the inert gas flow rate during the primary inert gas rotary blowing refining is preferably 1-3L/min, and can be specifically 1, 1.5, 2, 2.5 or 3L/min in the embodiment; the blowing time in the primary inert gas rotary blowing refining is preferably 4-10 min, and in the embodiment, the blowing time can be specifically 4, 5, 6, 7, 8, 9 or 10min.
In embodiments of the present invention, the temperature of the melt during the primary inert gas rotary blowing refining may be specifically 720, 725, 730, 735, 740, 745 or 750 ℃.
After purified Mg-Al-Zn melt is obtained, yttrium source is added into the purified Mg-Al-Zn melt to melt at the temperature of 730-760 ℃ to obtain the Mg-Al-Zn-Y melt. After the primary inert gas rotary blowing refining, the yttrium source is preferably added to melt at the temperature of 730-760 ℃, and the yttrium source can be specifically 730, 740, 750 or 760 ℃ in the embodiment. The kind of the yttrium source is not particularly limited in the present invention, and yttrium sources known to those skilled in the art may be used, for example, magnesium yttrium master alloy. In the present invention, the yttrium source is preferably preheated prior to melting, the preheating being preferably at a temperature of 180 to 200 ℃, and may specifically be 180, 190 or 200 ℃.
After the Mg-Al-Zn-Y melt is obtained, the invention carries out secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain the purified Mg-Al-Zn-Y melt. In the embodiment of the invention, the secondary inert gas rotary blowing refining is performed by using inert gas rotary blowing equipment, and the type of the inert gas rotary blowing equipment is not particularly limited. In the present invention, the inert gas is preferably helium or argon. In the invention, the rotating speed of the spray head is preferably 100-200 r/min during the rotary blowing refining of the secondary inert gas, and can be specifically 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200r/min in the embodiment; the inert gas flow rate during the secondary inert gas rotary blowing refining is preferably 1-3L/min, and can be specifically 1, 1.5, 2, 2.5 or 3L/min in the embodiment; the blowing time in the rotary blowing refining of the secondary inert gas is preferably 8-15 min, and in the embodiment, the blowing time can be specifically 8, 9, 10, 11, 12, 13, 14 or 15min.
In embodiments of the present invention, the temperature of the melt during the secondary inert gas rotary blowing refining may be specifically 680, 690, 700, 710 or 720 ℃.
After the secondary inert gas is subjected to rotary blowing refining, a lithium source is added into the purified Mg-Al-Zn-Y melt to melt, so that the Mg-Al-Zn-Y-Li melt is obtained. The kind of the lithium source is not particularly limited in the present invention, and a lithium source well known to those skilled in the art may be used, for example, pure lithium. In embodiments of the present invention, it is preferred to use a lithium shield to force pure lithium into the melt 2/3 below the melt surface to completely melt it. After the secondary inert gas rotary blowing refining, the lithium source is preferably added to melt at the temperature of 660-720 ℃ in the method, and the lithium source can be particularly 660, 670, 680, 690, 700, 710 or 720 ℃ in the embodiment.
After the Mg-Al-Zn-Y-Li melt is obtained, the invention adopts a refining flux to refine the Mg-Al-Zn-Y-Li melt at 660-720 ℃. In embodiments of the present invention, the temperature of the melt at the time of the tertiary flux refining may be specifically 660, 670, 680, 690, 700, 710 or 720 ℃.
In the invention, the refining flux comprises the following components in percentage by mass: 35-55% of potassium bromide, 10-35% of calcium chloride, 5-20% of lithium chloride, 5-15% of lithium fluoride, 1-10% of yttrium chloride and 2-15% of carbonate foaming agent.
In the present invention, the refining flux comprises 35 to 55wt% potassium bromide, and in embodiments may be specifically 35, 40, 45, 50 or 55wt%. In the invention, the potassium bromide acts as a thickener to increase the viscosity of the liquid flux.
In the present invention, the refining flux comprises 10 to 35wt% calcium chloride, and in embodiments may be specifically 10, 15, 20, 25, 30 or 35wt%. In the invention, the calcium chloride has the function of increasing the viscosity of the flux, and has the function of a thickening agent, so that slag can be gathered.
In the present invention, the refining flux comprises 5 to 20wt% lithium chloride, and in embodiments may be specifically 5, 10, 15 or 20wt%. In the present invention, the lithium chloride serves to wet the melt and aggregate inclusions.
In the present invention, the refining flux comprises 5 to 15wt% lithium fluoride, and in embodiments may be specifically 5,6, 7, 8, 9, 10, 11, 12, 13, 14, or 15wt%. In the present invention, the lithium fluoride functions to wet the melt and aggregate inclusions.
In the present invention, the refining flux comprises yttrium chloride in an amount of 1 to 10wt%, and in embodiments may be specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10wt%.
In the present invention, the refining flux comprises 2 to 15wt% carbonate blowing agent, which in embodiments may be specifically 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15wt%. In the present invention, the carbonate foaming agent is preferably one or more of lithium carbonate, calcium carbonate and potassium carbonate, and may be specifically one or two; when two types are used, lithium carbonate and potassium carbonate are preferable, and the mass ratio of the lithium carbonate to the potassium carbonate is preferably 1:1.
In the invention, yttrium chloride can compensate the burning loss of yttrium element, lithium chloride and lithium fluoride can compensate the burning loss of lithium element, and the component stability of the prepared magnesium-lithium alloy is improved. Under the high temperature condition, the carbonate foaming agent is heated and decomposed to generate carbon dioxide gas, and bubbles are formed. On the one hand, the bubbles enable the covering flux to float on the surface of the melt, and not sink into the melt, so that the covering and protecting effects can be maintained for a long time, and the usage amount of the flux is reduced; on the other hand, these bubbles react with magnesium and also have the effect of preventing the oxidation burn-out of the melt when covered on the surface of the melt.
In the present invention, the amount of the refining flux added is preferably 1 to 6% by mass of the Mg-Al-Zn-Y-Li melt, and may be specifically 1,2,3,4, 5 or 6%.
In the present invention, the time of the tertiary flux refining is preferably 5 to 10 minutes, and may be specifically 5, 6, 7, 8, 9 or 10 minutes; the holding temperature is preferably 660-720℃and may in particular be 660, 670, 680, 690, 700, 710 or 720 ℃.
After the tertiary flux is refined, the obtained purified Mg-Al-Zn-Y-Li melt is preferably cast to obtain an alloy casting blank; and carrying out solution treatment on the alloy casting blank, and then carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
After the three-stage refining, the temperature of the purified Mg-Al-Zn-Y-Li melt is preferably controlled to 680-720 ℃, and can be 680, 690, 700, 710 or 720 ℃ specifically, the covering solvent on the surface is removed, and the obtained purified Mg-Al-Zn-Y-Li melt is cast to obtain an alloy casting blank. The casting mold is not particularly limited, and may be a steel mold in the embodiment of the present invention. In the present invention, the mold is preferably preheated, and the temperature of the preheating may be specifically 200 ℃.
After the alloy casting blank is obtained, the alloy casting blank is subjected to solution treatment and then water quenching to obtain the T4-state magnesium-lithium alloy. In the present invention, the temperature of the solution treatment is preferably 300 to 350 ℃; the heat preservation time of the solution treatment is preferably 2 to 6 hours. The water quenching method is not particularly limited, and water quenching technical schemes well known to those skilled in the art can be adopted.
It should be noted that, without conflict, the following embodiments and features in the embodiments may be combined with each other; and, based on the embodiments in this disclosure, all other embodiments that may be made by one of ordinary skill in the art without inventive effort are within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present disclosure, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
Example 1
Mixing the alloy comprising Li 6%, al 1%, zn 1%, Y0.2% and the balance of magnesium according to the weight percentage, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 200 ℃, firstly melting a magnesium source, and then adding pure aluminum and pure zinc to melt at the temperature of 700 ℃ of a magnesium melt to obtain a Mg-Al-Zn melt;
Before adding the magnesium-yttrium intermediate alloy, when the temperature of the Mg-Al-Zn melt is 750 ℃, carrying out primary argon rotary blowing refining on the obtained Mg-Al-Zn melt by using an argon gas rotary blowing device: the rotating speed of the spray head is 200r/min, the gas flow is 1L/min, and the spraying time is 10min;
Adding preheated magnesium-yttrium intermediate alloy at 740 ℃ for melting after primary argon rotary blowing refining to obtain Mg-Al-Zn-Y melt;
before adding Li element, when the temperature is 720 ℃, utilizing argon gas rotary blowing equipment to carry out secondary argon rotary blowing refining on the Mg-Al-Zn-Y melt: the rotating speed of the spray head is 100r/min, the gas flow is 3L/min, and the spraying time is 8min;
And (3) pressing pure lithium into a position 2/3 below the liquid surface of the melt by adopting a lithium cover at 700 ℃ to completely melt the pure lithium to obtain a Mg-Al-Zn-Y-Li melt, and carrying out three-stage flux refining on the Mg-Al-Zn-Y-Li melt by using a refining flux at 720 ℃ for 5 minutes, wherein the adding amount of the refining flux is 1% of the mass of the Mg-Al-Zn-Y-Li melt. The composition of the refining flux is as follows: 35wt% potassium bromide, 35wt% calcium chloride, 20wt% lithium chloride, 5wt% lithium fluoride, 1wt% yttrium chloride and 4wt% lithium carbonate;
After refining, controlling the temperature to 720 ℃, removing covering flux on the surface of the melt, and casting the melt to a steel die preheated to about 200 ℃ to obtain the Mg-6Li-1Al-1Zn-0.2Y alloy casting blank.
And carrying out solution treatment (300 ℃ C. For 6 h) on the obtained Mg-6Li-1Al-1Zn-0.2Y alloy casting blank, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in table 1.
TABLE 1 chemical element composition (wt%) of the T4-state magnesium lithium alloy obtained in example 1
| Li | Al | Zn | Y | Impurity element | Mg |
| 5.86 | 1.02 | 0.83 | 0.21 | <0.0015 | Allowance of |
Example 2
Mixing the components and the alloy with the weight percentages of Li 14%, al 5%, zn 5%, Y1.5% and the balance of magnesium, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 180 ℃, firstly melting a magnesium source, and then adding pure aluminum and pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt;
Before adding the magnesium-yttrium intermediate alloy, when the temperature of the Mg-Al-Zn melt is 720 ℃, carrying out primary argon rotary blowing refining on the obtained Mg-Al-Zn melt by using an argon gas rotary blowing device: the rotating speed of the spray head is 100r/min, the gas flow is 3L/min, and the spraying time is 4min;
adding preheated magnesium-yttrium intermediate alloy to melt at 700 ℃ after primary argon rotary blowing refining to obtain Mg-Al-Zn-Y melt;
before adding Li element, when the temperature is 680 ℃, carrying out secondary argon rotary blowing refining on the Mg-Al-Zn-Y melt by using argon rotary blowing equipment: the rotating speed of the spray head is 100r/min, the gas flow is 3L/min, and the spraying time is 8min;
And (3) pressing pure lithium into a position 2/3 below the liquid surface of the melt by adopting a lithium cover at 660 ℃ to completely melt the pure lithium to obtain a Mg-Al-Zn-Y-Li melt, and carrying out tertiary flux refining on the Mg-Al-Zn-Y-Li melt by utilizing a refining flux at 660 ℃, wherein the adding amount of the refining flux is 6% of the mass of the Mg-Al-Zn-Y-Li melt. The composition of the refining flux is as follows: 55wt% of potassium bromide, 10wt% of calcium chloride, 5wt% of lithium chloride, 15wt% of lithium fluoride, 10wt% of yttrium chloride, 5wt% of potassium carbonate;
After refining, controlling the temperature to 680 ℃, removing covering flux on the surface of the melt, and casting the melt to a steel die preheated to about 200 ℃ to obtain the Mg-14Li-5Al-5Zn-1.5Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-14Li-5Al-5Zn-1.5Y alloy casting blank at the temperature of 300 ℃ for 6 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 2.
TABLE 2 chemical element composition (wt%) of the T4-state magnesium lithium alloy obtained in example 2
| Li | Al | Zn | Y | Impurity element | Mg |
| 13.89 | 5.01 | 4.88 | 1.46 | <0.0015 | Allowance of |
Example 3
Mixing the components and the alloy with the weight percentage of Li 8%, al 3%, zn 2%, Y0.5% and the balance of magnesium, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 190 ℃, firstly melting a magnesium source, and then adding pure aluminum and pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt;
Before adding the magnesium-yttrium intermediate alloy, when the temperature of the Mg-Al-Zn melt is 735 ℃, carrying out primary argon rotary blowing refining on the obtained Mg-Al-Zn melt by using an argon gas rotary blowing device: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 7min;
adding preheated magnesium-yttrium intermediate alloy at 720 ℃ for melting after primary argon rotary blowing refining to obtain Mg-Al-Zn-Y melt;
Before adding Li element, when the temperature is 700 ℃, utilizing argon gas rotary blowing equipment to carry out secondary argon rotary blowing refining on the Mg-Al-Zn-Y melt: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 11min;
And (3) pressing pure lithium into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 680 ℃ to completely melt the pure lithium to obtain an Mg-Al-Zn-Y-Li melt, and carrying out three-stage flux refining on the Mg-Al-Zn-Y-Li melt by utilizing a refining flux at 690 ℃ for 7 minutes, wherein the adding amount of the refining flux is 3.5% of the mass of the Mg-Al-Zn-Y-Li melt. The composition of the refining flux is as follows: 45wt% of potassium bromide, 20wt% of calcium chloride, 15wt% of lithium chloride, 10wt% of lithium fluoride, 5wt% of yttrium chloride and 5wt% of calcium carbonate;
After refining, controlling the temperature to 700 ℃, removing covering flux on the surface of the melt, casting the melt into a steel die preheated to about 200 ℃, and obtaining the Mg-8Li-3Al-2Zn-0.5Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-8Li-3Al-2Zn-0.5Y alloy casting blank at the temperature of 350 ℃ for 2 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 3.
TABLE 3 chemical element composition (wt%) of the T4-state magnesium-lithium alloy obtained in example 3
| Li | Al | Zn | Y | Impurity element | Mg |
| 7.96 | 3.01 | 1.94 | 0.46 | <0.0015 | Allowance of |
Example 4
Preparing the alloy with the components and the weight percentages of Li 10%, al 4%, zn 1%, Y1% and the balance of magnesium, preheating the pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 200 ℃, firstly melting a magnesium source, and then adding the pure aluminum and the pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt;
Before adding the magnesium-yttrium intermediate alloy, when the temperature of the Mg-Al-Zn melt is 730 ℃, carrying out primary argon rotary blowing refining on the obtained Mg-Al-Zn melt by utilizing an argon gas rotary blowing device: the rotating speed of the spray head is 200r/min, the gas flow is 2L/min, and the spraying time is 6min;
adding preheated magnesium-yttrium intermediate alloy at 710 ℃ for melting after primary argon rotary blowing refining to obtain Mg-Al-Zn-Y melt;
Before adding Li element, when the temperature is 690 ℃, using argon gas rotary blowing equipment to carry out secondary argon gas rotary blowing refining on the obtained Mg-Al-Zn-Y melt: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 10min;
And (3) pressing pure lithium into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 670 ℃ to completely melt the pure lithium to obtain an Mg-Al-Zn-Y-Li melt, and carrying out three-stage flux refining on the Mg-Al-Zn-Y-Li melt by utilizing a refining flux at 690 ℃ for 7 minutes, wherein the adding amount of the refining flux is 3% of the mass of the Mg-Al-Zn-Y-Li melt. The composition of the refining flux is as follows: 45wt% of potassium bromide, 15wt% of calcium chloride, 10wt% of lithium chloride, 9wt% of lithium fluoride, 6wt% of yttrium chloride, 15wt% of lithium carbonate and potassium carbonate (the mass ratio of the two is 1:1);
After refining, controlling the temperature to 700 ℃, removing covering flux on the surface of the melt, and casting the melt to a steel die preheated to about 200 ℃ to obtain the Mg-10Li-4Al-1Zn-1Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-10Li-4Al-1Zn-1Y alloy casting blank at the temperature of 325 ℃ for 4 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 4.
TABLE 4 chemical element composition (wt%) of the T4-state magnesium-lithium alloy obtained in example 4
| Li | Al | Zn | Y | Impurity element | Mg |
| 9.91 | 3.91 | 0.91 | 0.88 | <0.0015 | Allowance of |
Example 5
Preparing materials according to the components and the alloy with the weight percentage of Li 9%, al 3%, zn 2% and Y0.8% and the balance of magnesium, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 180 ℃, firstly melting a magnesium source, and then adding pure aluminum and pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt;
Before adding the magnesium-yttrium intermediate alloy, when the temperature of the Mg-Al-Zn melt is 730 ℃, carrying out primary argon rotary blowing refining on the obtained Mg-Al-Zn melt by utilizing an argon gas rotary blowing device: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 7min;
adding preheated magnesium-yttrium intermediate alloy at 720 ℃ for melting after primary argon rotary blowing refining to obtain Mg-Al-Zn-Y melt;
Before adding Li element, when the temperature is 680 ℃, using argon gas rotary blowing equipment to carry out secondary argon gas rotary blowing refining on the obtained Mg-Al-Zn-Y melt: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 10min;
And (3) pressing pure lithium into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 670 ℃ to completely melt the pure lithium to obtain an Mg-Al-Zn-Y-Li melt, and carrying out three-stage flux refining on the Mg-Al-Zn-Y-Li melt by utilizing a refining flux at 690 ℃ for 7 minutes, wherein the adding amount of the refining flux is 2% of the mass of the Mg-Al-Zn-Y-Li melt. The composition of the refining flux is as follows: 55wt% of potassium bromide, 10wt% of calcium chloride, 5wt% of lithium chloride, 15wt% of lithium fluoride, 10wt% of yttrium chloride, 5wt% of lithium carbonate; after refining, the temperature is controlled at 690 ℃, covering flux on the surface of the melt is removed, and the melt is cast into a steel die preheated to about 200 ℃ to obtain a Mg-9Li-3Al-2Zn-0.8Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-9Li-3Al-2Zn-0.8Y alloy casting blank at the temperature of 300 ℃ for 6 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 5.
TABLE 5 chemical element composition (wt%) of the T4-state magnesium-lithium alloy obtained in example 5
| Li | Al | Zn | Y | Impurity element | Mg |
| 8.79 | 3.02 | 1.93 | 0.71 | <0.0015 | Allowance of |
Comparative example 1
Preparing materials according to the components and the alloy with the weight percentage of Li 9%, al 3%, zn 2% and Y0.8% and the balance of magnesium, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 200 ℃, firstly melting a magnesium source, then adding pure aluminum and pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt, and then adding magnesium yttrium intermediate alloy to melt at the temperature of the Mg-Al-Zn melt of 730 ℃ to obtain a Mg-Al-Zn-Y melt;
the pure lithium is pressed into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 680 ℃ to be completely melted, and after the Li element is added, the obtained Mg-Al-Zn-Y-Li melt is subjected to primary argon rotary blowing refining by utilizing an argon rotary blowing device at 680 ℃: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 10min;
After refining, controlling the temperature to 690 ℃, casting the melt into a steel die preheated to about 200 ℃, and obtaining an Mg-9Li-3Al-2Zn-0.8Y alloy casting blank;
And (3) carrying out solution treatment on the obtained Mg-9Li-3Al-2Zn-0.8Y alloy casting blank at the temperature of 350 ℃ for 2 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 6.
TABLE 6 chemical element composition (wt%) of the T4-state magnesium lithium alloy obtained in comparative example 1
| Li | Al | Zn | Y | Impurity element | Mg |
| 8.39 | 2.89 | 1.87 | 0.68 | <0.0015 | Allowance of |
Comparative example 2
Preparing materials according to the components and the alloy with the weight percentage of Li 9%, al 3%, zn 2% and Y0.8% and the balance of magnesium, preheating pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 200 ℃, firstly melting a magnesium source, then adding pure aluminum and pure zinc to melt at the temperature of the magnesium melt of 700 ℃ to obtain a Mg-Al-Zn melt, and then adding magnesium yttrium intermediate alloy to melt at the temperature of the Mg-Al-Zn melt of 730 ℃ to obtain a Mg-Al-Zn-Y melt;
Before adding Li element, when the temperature is 730 ℃, using argon gas rotary blowing equipment to carry out primary argon rotary blowing refining on the obtained Mg-Al-Zn-Y melt: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 7min;
The pure lithium is pressed into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 680 ℃ to be completely melted, and after the Li element is added, the obtained Mg-Al-Zn-Y-Li melt is subjected to secondary argon rotary blowing refining by utilizing an argon rotary blowing device at 680 ℃: the rotating speed of the spray head is 150r/min, the gas flow is 2L/min, and the spraying time is 10min;
After refining, controlling the temperature to 690 ℃, casting the melt into a steel die preheated to about 200 ℃, and obtaining the Mg-9Li-3Al-2Zn-0.8Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-9Li-3Al-2Zn-0.8Y alloy casting blank at the temperature of 350 ℃ for 2 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 7.
TABLE 7 chemical element composition (wt%) of the T4-state magnesium lithium alloy obtained in comparative example 2
| Li | Al | Zn | Y | Impurity element | Mg |
| 8.58 | 2.91 | 1.89 | 0.65 | <0.0015 | Allowance of |
Comparative example 3
Mixing the components and the alloy with the weight percentages of Li 9%, al 3%, zn 2% and Y0.8% and the balance of magnesium, preheating the pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy to 200 ℃, and putting the preheated pure magnesium, pure aluminum, pure zinc and magnesium yttrium intermediate alloy into a crucible for melting to obtain Mg-Al-Zn-Y melt;
Pure lithium is pressed into a position 2/3 below the liquid level of the melt by adopting a lithium cover at 680 ℃ to be completely melted, and after Li element is added, refining is carried out by utilizing a refining flux with the addition amount of 2 percent of the mass of the Mg-Al-Zn-Y-Li melt at 680 ℃. The composition of the refining flux is as follows: 55wt% of potassium bromide, 10wt% of calcium chloride, 5wt% of lithium chloride, 16wt% of lithium fluoride, 12wt% of yttrium chloride, 2wt% of lithium carbonate;
After refining, the temperature is controlled at 690 ℃, covering flux on the surface of the melt is removed, and the melt is cast into a steel die preheated to about 200 ℃ to obtain a Mg-9Li-3Al-2Zn-0.8Y alloy casting blank.
And (3) carrying out solution treatment on the obtained Mg-9Li-3Al-2Zn-0.8Y alloy casting blank at the temperature of 350 ℃ for 2 hours, and finally carrying out water quenching to obtain the T4-state magnesium-lithium alloy.
The chemical composition analysis of the obtained T4-state magnesium-lithium alloy is carried out, and the results are shown in Table 8.
TABLE 8 chemical element composition (wt%) of the T4-state magnesium-lithium alloy obtained in comparative example 3
| Li | Al | Zn | Y | Impurity element | Mg |
| 8.47 | 2.87 | 1.91 | 0.70 | <0.0015 | Allowance of |
Test results
The invention adopts GB/T228.1-2010 section 1 of tensile test of metallic materials: room temperature test method the room temperature mechanical properties of the solid solution Mg-Li-Al-Zn-Y alloys obtained by the solid solution treatment of examples and comparative examples were measured, and the results are shown in table 9.
TABLE 9 room temperature mechanical Properties of solid solution Mg-Li-Al-Zn-Y alloys of examples and comparative examples of the present invention
The invention adopts GB/T13748.15-2005 test method of magnesium and magnesium alloy chemical analysis method to measure slag content, element burning loss rate and sedimentation rate of T4-state magnesium-lithium alloy obtained in examples and comparative examples, and the results are shown in Table 10.
TABLE 10 slag content, li burn-out Rate and Y Settlement Rate of T4-state magnesium-lithium alloys obtained in examples and comparative examples of the present invention
| Examples | Slag content (vol%) | Li element burn-out rate (%) | Sedimentation rate of Y element (%) |
| 1 | 0.273 | 9.3 | 12.8 |
| 2 | 0.283 | 9.5 | 13.2 |
| 3 | 0.226 | 8.9 | 12.2 |
| 4 | 0.235 | 9.2 | 13.4 |
| 5 | 0.263 | 9.4 | 12.8 |
| Comparative example 1 | 1.086 | 29.8 | 32.1 |
| Comparative example 2 | 0.887 | 23.5 | 31.2 |
| Comparative example 3 | 1.123 | 27.4 | 31.9 |
The embodiment and the comparative example show that the method provided by the invention can obviously reduce the burning loss of noble elements Li and Y, greatly reduce the content of melt inclusions, effectively improve the quality of the magnesium-lithium alloy, reduce the production cost of the magnesium-lithium alloy and promote the popularization and application of the materials.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (7)
1. The smelting and purifying method of the Mg-Li-Al-Zn-Y alloy for three-dimensional printing is characterized by comprising the following steps of:
According to the composition of the Mg-Li-Al-Zn-Y alloy, firstly melting a magnesium source, adding an aluminum source and a zinc source at 680-700 ℃ into the magnesium melt for melting to obtain a Mg-Al-Zn melt;
carrying out primary inert gas rotary blowing refining on the Mg-Al-Zn melt at the temperature of 720-750 ℃ to obtain purified Mg-Al-Zn melt;
adding yttrium source into the purified Mg-Al-Zn melt to melt at the temperature of 730-760 ℃ to obtain Mg-Al-Zn-Y melt;
Performing secondary inert gas rotary blowing refining on the Mg-Al-Zn-Y melt at 680-720 ℃ to obtain purified Mg-Al-Zn-Y melt;
Adding a lithium source into the purified Mg-Al-Zn-Y melt for melting to obtain a Mg-Al-Zn-Y-Li melt;
When the temperature of the melt is 660-720 ℃, adopting a refining flux to refine the Mg-Al-Zn-Y-Li melt by a tertiary flux to obtain a purified Mg-Al-Zn-Y-Li melt;
casting the purified Mg-Al-Zn-Y-Li melt to obtain an alloy casting blank;
carrying out solution treatment on the alloy casting blank, and then carrying out water quenching to obtain a T4-state magnesium-lithium alloy;
the aluminum source is pure aluminum, and the zinc source is pure zinc;
the temperature of the solid solution treatment is 300-350 ℃; the heat preservation time of the solution treatment is 2-6 h;
The conditions of the primary inert gas rotary blowing refining comprise: the rotating speed of the spray head is 100-200 r/min, the flow rate of the inert gas is 1-3L/min, and the spraying time is 4-10 min;
the conditions of the secondary inert gas rotary blowing refining comprise: the rotating speed of the spray head is 100-200 r/min, the flow rate of the inert gas is 1-3L/min, and the spraying time is 8-15 min;
The refining flux comprises the following components in percentage by mass: 35-55% of potassium bromide, 10-35% of calcium chloride, 5-20% of lithium chloride, 5-15% of lithium fluoride, 1-10% of yttrium chloride and 2-15% of carbonate foaming agent.
2. The smelting purification method according to claim 1, wherein the addition amount of the refining flux is 1 to 6% by mass of the Mg-Al-Zn-Y-Li melt.
3. The smelting purification process of claim 1, wherein the carbonate blowing agent is one or more of lithium carbonate, calcium carbonate, and potassium carbonate.
4. The smelting purification process according to claim 1, wherein the Mg-Li-Al-Zn-Y alloy comprises the following elemental composition in mass percent: 6 to 14 percent of Li, 1 to 5 percent of Al, 1 to 5 percent of Zn, 0.2 to 1.5 percent of Y and the balance of Mg.
5. The smelting purification process according to claim 1, wherein the tertiary flux refining time is 5 to 10 minutes and the holding temperature is 660 to 720 ℃.
6. The smelting purification process according to claim 1, wherein the temperature of the purified Mg-Al-Zn-Y melt is 660 to 720 ℃ when the lithium source is added.
7. The smelting purification process of claim 1, wherein the magnesium source, aluminum source, zinc source, and yttrium source further comprise preheating prior to melting, the preheating being at a temperature of 180-200 ℃.
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| CN106834843A (en) * | 2017-02-20 | 2017-06-13 | 鼎镁（昆山）新材料科技有限公司 | A kind of high-strength ultralight two phase structure magnesium lithium alloy sheet material and preparation method thereof |
| CN108384974A (en) * | 2018-01-22 | 2018-08-10 | 上海交通大学 | A kind of melt refining flux of the magnesium lithium alloy containing rare earth and preparation method thereof |
| CN113174506A (en) * | 2021-04-08 | 2021-07-27 | 上海交通大学 | Refining flux suitable for magnesium-lithium alloy and preparation method thereof |
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| CN106957979A (en) * | 2017-04-28 | 2017-07-18 | 苏州轻金三维科技有限公司 | A kind of long-periodic structure enhancing magnesium lithium alloy and preparation method thereof |
| CN114045408A (en) * | 2021-11-10 | 2022-02-15 | 中北大学 | Preparation method of high-performance Mg-Y-Zn-Li magnesium alloy suitable for engineering structural member |
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| CN108384974A (en) * | 2018-01-22 | 2018-08-10 | 上海交通大学 | A kind of melt refining flux of the magnesium lithium alloy containing rare earth and preparation method thereof |
| CN113174506A (en) * | 2021-04-08 | 2021-07-27 | 上海交通大学 | Refining flux suitable for magnesium-lithium alloy and preparation method thereof |
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