CN115652155A - Efficient grain refiner for rare earth magnesium alloy, preparation method and use method thereof - Google Patents
Efficient grain refiner for rare earth magnesium alloy, preparation method and use method thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 110
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 75
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 97
- 238000010008 shearing Methods 0.000 claims abstract description 59
- 239000011777 magnesium Substances 0.000 claims abstract description 54
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 48
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000007670 refining Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
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- 238000010899 nucleation Methods 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims description 140
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 94
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 84
- 229910052726 zirconium Inorganic materials 0.000 claims description 59
- 239000000155 melt Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims description 25
- 238000007711 solidification Methods 0.000 claims description 22
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- 238000005266 casting Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 238000009749 continuous casting Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
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- 238000010128 melt processing Methods 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000006104 solid solution Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 229910000946 Y alloy Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000000527 sonication Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
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Abstract
The invention provides a high-efficiency grain refiner for rare earth magnesium alloy, a preparation method and a using method thereof. The high-speed shearing melt processing method and the ultrasonic processing adopted by the invention can uniformly distribute the Ti, zr or Ti/Zr powder with high mass fraction in the magnesium matrix, improve the content of Ti, zr or Ti/Zr in the grain refiner compared with the traditional method, uniformly distribute Ti, zr or Ti/Zr, reduce the agglomeration and growth of nucleation particles, and improve the utilization rate and the refining effect of the refiner.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy grain refinement, and particularly relates to an efficient grain refiner for rare earth magnesium alloy, a preparation method and a use method thereof.
Background
The rare earth magnesium alloy has excellent performances of high temperature resistance, high strength, high toughness and the like, has wide application prospect on parts such as aircraft cabins, satellite structural members, airship frames, engine covers, engine cylinder bodies, gearbox casings and the like, and is highly concerned. However, the natural contradiction exists between the rare earth magnesium alloy melt purification and the grain refinement under the condition of large smelting amount in engineering application. The magnesium alloy is refined by adopting the traditional magnesium-zirconium intermediate alloy form, the problems of high loss rate and poor refining effect exist, the strengthening and toughening level of the magnesium alloy is greatly limited, and the application of the magnesium alloy as a lightweight material on an aircraft is hindered.
Zr is the most effective grain refiner for magnesium alloys other than Al, mn, si, etc. Zr can reduce the hot-violent tendency and improve the obdurability of the alloy. The Zr in magnesium alloys is usually added in the form of Mg-Zr master alloys. The master alloy is typically reduced with Mg to reduce K 2 ZrF 2 The Mg-Zr intermediate alloy produced by the method has more slag inclusion. The patent application discloses a magnesium-zirconium intermediate alloy and a production method thereof (CN 10354077A), a secondary smelting method for producing the magnesium-zirconium intermediate alloy (CN 101845564A) and a method for preparing the magnesium-zirconium intermediate alloy by ultrasonic treatment (CN 105385863B), which are all traditional Mg-Zr intermediate alloy preparation methods. The Zr prepared by the method has low yield, low content of effective active nucleation Zr particles, poor refining effect and enough Zr obtained by adding several times of Zr in the production due to the spontaneous precipitation of ZrAmount, whereas the actual ingot only needs less than 1% Zr. And the Mg-Zr intermediate alloy prepared by the traditional method also contains more impurities, a large amount of solvent is needed for sedimentation, and the added large amount of flux can introduce inclusion defects, so that the performance of the rare earth magnesium alloy is reduced.
Research shows that Ti atoms can be partially polymerized at the front edge of a solid-liquid interface to cause component supercooling, inhibit grain growth and have strong grain refinement capability. The Ti element has very large potential as a high-efficiency grain refiner of the magnesium alloy because the growth inhibition factor of Ti is 59500, the crystal structures of alpha-Ti and Mg are all close-packed hexagonal, the lattice constant of the alpha-Ti is close to that of the Mg, the alpha-Ti has good coherent relation with the Mg, and the Ti element can be a high-quality heterogeneous nucleation core of the Mg from the crystallographic point of view. However, ti is difficult to be added into the magnesium alloy independently, the melting point of Ti is even larger than that of Mg, the loss of directly adding pure Ti is large, and the process is complex. Therefore, the Ti-containing intermediate alloy has a lower melting point than pure Ti and improves the practical yield of the alloy elements. But at present, no effective method is available for realizing the addition of Ti, so that the grain refining effect of the rare earth magnesium alloy is limited. Therefore, there is a need to develop a more efficient and effective method for preparing grain refiners to improve the performance level of magnesium alloy materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor of the invention carries out intensive research and provides a high-efficiency grain refiner for rare earth magnesium alloy, a preparation method and a using method thereof.
The technical scheme provided by the invention is as follows:
in a first aspect, a preparation method of an efficient grain refiner for rare earth magnesium alloy comprises the following steps: adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt or a semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic waves, and solidifying to prepare a grain refiner for the rare earth magnesium alloy;
when the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into a pure magnesium melt to prepare the grain refiner for the rare earth magnesium alloy, the preparation method specifically comprises the following steps: heating pure magnesium to a complete molten state to obtain a pure magnesium melt; then adding the weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into the pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain the magnesium melt with uniformly distributed titanium-containing element or zirconium-containing element or titanium/zirconium-containing element; then pouring the melt into a mold, solidifying under the action of pressure, preparing a grain refiner for the rare earth magnesium alloy after complete solidification, and carrying out the whole preparation process under the protection of a vacuum environment or inert atmosphere;
when the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into the semi-solid molten magnesium alloy to prepare the grain refiner for the rare earth magnesium alloy, the preparation method specifically comprises the following steps: heating pure magnesium alloy to a semi-solid state, adding weighed and fully preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a completely molten state after all the powder is added, applying high-speed shearing and ultrasonic treatment to obtain a magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated die, solidifying under the action of pressure, preparing a grain refiner for rare earth magnesium alloy after complete solidification, and performing the whole preparation process under the protection of a vacuum environment or an inert atmosphere.
In a second aspect, the efficient grain refiner for rare earth magnesium alloy is prepared according to the preparation method of the efficient grain refiner for rare earth magnesium alloy in the first aspect, wherein the grain size of active nucleation Ti or Zr or (Ti/Zr) in the efficient grain refiner for rare earth magnesium alloy is 85-99.9% and is smaller than 5 μm.
In a third aspect, a method for using an efficient grain refiner for rare earth magnesium alloy is characterized by comprising the following steps: weighing raw materials with corresponding weight according to the components and the mass percentage of the magnesium alloy, adding the grain refiner in the second aspect after the raw materials are completely melted and skimmed, fishing out the bottom and stirring after the raw materials are completely melted, and then refining; and after refining, removing slag, standing, and using the prepared melt for rare earth magnesium alloy casting preparation or rare earth magnesium alloy semi-continuous ingot preparation.
According to the efficient grain refiner for the rare earth magnesium alloy, the preparation method and the use method thereof, the efficient grain refiner has the following beneficial effects:
1. compared with the traditional molten salt method, the Mg-Ti, mg-Zr, mg-Ti/Zr, mg-TM-Ti, mg-TM-Zr or Mg-TM-Ti/Zr grain refiner prepared by the invention contains Zr, ti or Ti/Zr with higher content, and the mass fraction reaches 30-70%. And has a higher content of fine uniform nucleation particles, with the particle size of Ti or Zr or (Ti/Zr) being 85% -99.9% less than 5 μm.
2. The growth inhibition factor of Ti is 59500, the lattice constant of Ti is close to that of Mg, and Ti has a good coherent relation with Mg, and is a very efficient grain refiner. The Mg-Ti or Mg-TM-Ti and Mg-Ti/Zr or Mg-TM-Ti/Zr efficient grain refiner prepared by the invention contains a large amount of fine active nucleation Ti particles or Ti/Zr particles, the growth inhibition factor of Ti and Ti/Zr is more than 1500 times of that of Zr, and the grain refiner has more excellent grain refining capability.
3. As Ti and Zr can form a Ti/Zr infinite solid solution, the Mg-Ti or Mg-Zr grain refiner is added compared with the Mg-Ti/Zr grain refiner, the degree of mismatching with the crystallographic plane of the basal plane of the magnesium substrate is reduced, the degree of lattice matching with the magnesium substrate is improved, the overcooling of the components is increased, the substrate and the second phase can be obviously refined, and the addition of Ti/Zr can reach the maximum addition of Zr.
4. The high-speed shearing melt processing method adopted by the invention can uniformly distribute high-quality-fraction Ti, zr or Ti/Zr powder in the magnesium matrix, and improves the content of Ti, zr or Ti/Zr in the grain refiner compared with the traditional method. The uniform distribution of Ti, zr or Ti/Zr can be further improved through high-speed shearing treatment, the agglomeration and growth of nucleation particles are reduced, and the utilization rate and the refining effect of the refiner are improved. And in the melt treatment, the particle size of Ti, zr or Ti/Zr can be further refined through high-speed shearing, large particles are crushed to be micron-sized or even nano-sized, and the content of fine active nucleation particles is further improved.
5. The Mg-TM-Ti, mg-TM-Zr or Mg-TM-Ti/Zr grain refiner prepared by the invention has excellent quality. The uniform dispersion effect is further increased by high-speed shearing in the semi-solid region, and the ultrasonic treatment applied to the liquid region can not only further improve the dispersion effect, but also discharge a small amount of gas introduced in the high-speed shearing. Pressure is applied during the solidification process, and the internal defects of the grain refiner are further reduced. High-speed shearing treatment, ultrasonic treatment and pressure solidification, so that the prepared grain refiner has compact structure, and the defects of pores, shrinkage porosity, sand holes, refined particle agglomeration and the like are greatly reduced. The high-quality grain refiner can be well inherited into the rare earth magnesium alloy.
6. The Mg-Ti, mg-Zr, mg-Ti/Zr, mg-TM-Ti, mg-TM-Zr or Mg-TM-Ti/Zr grain refiner prepared by the invention has good component uniformity, more infinite solid solution particles of effective Ti, zr or Ti/Zr mixed uniformly, reduces the dosage of the grain refiner required to be added and can further reduce the manufacturing cost.
7. The Mg-Ti-Zr efficient grain refiner prepared by the invention has low inclusion content, greatly improves the purity of the rare earth magnesium alloy melt, reduces the time for standing the melt for deslagging, can obviously improve the melt purification effect, and has clean and tidy interface of the prepared rare earth magnesium alloy.
8. The Mg-Ti, mg-Zr, mg-Ti/Zr, mg-TM-Ti, mg-TM-Zr or Mg-TM-Ti/Zr prepared by the invention has a large amount of suspended fine Ti, zr or Ti/Zr particles, the settling speed is slow in the standing process, the problem of settlement and refinement recession of the original grain refiner is effectively solved, the casting or ingot casting prepared by using the novel grain refiner has fine grains, and the cast structure at each position is uniform.
9. A large amount of flux, namely covering agent and refining agent, is required to be added for deslagging in the smelting process of the rare earth magnesium alloy, and the refining agent only needs to be added once, so that the inclusion defect of the flux of a casting and an ingot is greatly reduced.
Drawings
FIG. 1 is a microstructure of a Mg-40Zr novel Mg-Zr grain refiner of example 1;
FIG. 2 is a microstructure of an as-cast Mg-6.5Gd-3.5Y-0.6Zr alloy in example 1;
FIG. 3 is the microstructure of the Mg-50Ti/Zr novel Mg-Zr grain refiner of example 2;
FIG. 4 is an as-cast Mg-6.5Gd-3.5Y-0.6Zr alloy microstructure treated with a conventional Mg-30Zr refiner in comparative example 1.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to the first aspect of the invention, the preparation method of the efficient grain refiner for the rare earth magnesium alloy is provided, and comprises the following steps: adding the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt or a semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic, and solidifying to obtain the grain refiner for the rare earth magnesium alloy. The average particle size of the titanium powder, the zirconium powder or the uniformly mixed titanium/zirconium powder is 0.001 to 1000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm.
In the invention, when preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into a pure magnesium melt to prepare the grain refiner for the rare earth magnesium alloy, the preparation method comprises the following steps: heating pure magnesium to a complete molten state to obtain a pure magnesium melt; then adding the weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into the pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain the magnesium melt with titanium element or zirconium element or titanium/zirconium element uniformly distributed; and then pouring the melt into a mold, solidifying under the action of pressure, preparing the grain refiner for the rare earth magnesium alloy after complete solidification, and carrying out the whole preparation process under the protection of a vacuum environment or an inert atmosphere.
In the embodiment, the preheating temperature of the titanium powder, the zirconium powder or the uniformly mixed titanium/zirconium powder is 300-600 ℃, and the preheating time is 30-90 min.
The specific adding mode of the powder is as follows: dividing the added powder into n parts, wherein n is more than or equal to 5 and less than or equal to 30, applying high-speed shearing for 30-90 s after every 1 part of the powder is added, the rotating speed of a rotor is 5000-20000 rpm, continuously applying high-speed shearing for 10-60 min after the powder is completely added, and then applying ultrasonic treatment, wherein the technological parameter of the ultrasonic treatment is 2000-5000 Hz, and the time of the ultrasonic treatment is 2-15 min.
The solidification process is to pour magnesium melt containing titanium or zirconium or titanium/zirconium into a metal mold with the preheating temperature of 300-600 ℃, apply the pressure of 60-150 MPa, and maintain the pressure for 5-30 min.
The components of the prepared efficient grain refiner for rare earth magnesium alloy are Mg- (30-70) Ti or Mg- (30-70) Zr or Mg- (30-70) (Ti/Zr) (wt.%).
In the invention, when the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into the semi-solid molten magnesium alloy to prepare the grain refiner for the rare earth magnesium alloy, the preparation method comprises the following steps: heating pure magnesium alloy to a semi-solid state, adding weighed and fully preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a completely molten state after all the powder is added, applying high-speed shearing and ultrasonic treatment to obtain a magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated die, solidifying under the action of pressure, preparing a grain refiner for rare earth magnesium alloy after complete solidification, and performing the whole preparation process under the protection of a vacuum environment or an inert atmosphere.
In the embodiment, the preheating temperature of the titanium powder, the zirconium powder or the uniformly mixed titanium/zirconium powder is 300-600 ℃, and the preheating time is 30-90 min.
The specific adding mode of the powder is as follows: dividing the added powder into n parts, wherein n is more than or equal to 5 and less than or equal to 30, and applying high-speed shearing for 30-120 s after adding 1 part of the powder, and the rotating speed of a rotor is 6000-20000 rpm; after the powder is completely added, continuously applying high-speed shearing at 6000 rpm-20000 rpm for 5 min-60 min; heating the magnesium alloy to a complete melting state, and applying high-speed shearing and ultrasonic treatment, wherein the rotating speed of a high-speed shearing rotor is 6000-20000 rpm, and the treatment time is 5-60 min; then ultrasonic treatment is carried out, the technological parameters of the ultrasonic treatment are 3000 Hz-5000 Hz, and the ultrasonic treatment time is 5 min-30 min.
The solidification process is to pour magnesium melt containing titanium or zirconium or titanium/zirconium into a metal mold with the preheating temperature of 300-600 ℃, apply the pressure of 80-150 MPa, and maintain the pressure for 5-30 min.
The semisolid magnesium alloy is Mg-TM system, wherein TM is one or a mixture of Zn, cu and Ni elements; the efficient grain refiner for the rare earth magnesium alloy comprises the components of Mg- (10-30) TM- (30-60) Ti, mg- (10-30) TM- (30-60) Zr or Mg- (10-30) TM- (30-60) (Ti/Zr) (wt.%). Preferably, the efficient grain refiner for the rare earth magnesium alloy comprises the components of Mg- (33-50) Ti or Mg- (33-50) Zr or Mg- (33-50) (Ti/Zr) (wt.%), preferably Mg-35Zr, mg-40Zr, mg-50Zr, mg-35 (Ti/Zr), mg-40 (Ti/Zr), mg-45 (Ti/Zr), mg-50Ti/Zr, mg-35Ti and Mg-40Ti; more preferably, the efficient grain refiner for rare earth magnesium alloy comprises Mg- (20-35) TM- (33-50) Ti, mg- (20-35) TM- (33-50) Zr or Mg- (20-35) TM- (33-50) (Ti/Zr) (wt.%), wherein TM is Zn, cu and Ni element. More preferably Mg-13.3Zn-33Zr, mg-20Zn-35Zr, mg-20Cu-35Zr, mg-15Cu-50Zr, mg-25Zn-35Ti, mg-25Ni-35Ti, mg-10Ni-50Zr, mg-20Zn-40 (Ti/Zr), mg-20Cu-40 (Ti/Zr), mg-20Ni-40 (Ti/Zr), mg-10Zn-5Cu-40 (Ti/Zr), mg-15Zn-15Ni-45 (Ti/Zr), mg-15Ni-15Cu-45 (Ti/Zr), mg-10Zn-50 (Ti/Zr).
According to a second aspect of the invention, the efficient grain refiner for the rare earth magnesium alloy is provided, which is prepared by the preparation method of the efficient grain refiner for the rare earth magnesium alloy according to the first aspect, wherein the grain refiner for the rare earth magnesium alloy has the active nucleation Ti or Zr or (Ti/Zr) particle size of 85-99.9% and is smaller than 5 μm.
According to a third aspect of the invention, a method for using a high-efficiency grain refiner for rare earth magnesium alloy is provided, which comprises the following steps: weighing raw materials with corresponding weight according to the components and the mass percentage of the magnesium alloy, adding the grain refiner of claim 9 after the raw materials are completely melted and skimmed, fishing out the bottom and stirring after the raw materials are completely melted, and then refining; and after refining, removing slag, standing, and using the prepared melt for rare earth magnesium alloy casting preparation or rare earth magnesium alloy semi-continuous ingot preparation.
Examples
Example 1
And (2) putting 30kg of preheated pure magnesium at the bottom of a crucible, heating and smelting, after the temperature of the melt is raised to 670-680 ℃ and the pure magnesium is completely melted, adding 20kg of zirconium powder with the average grain size of 30 mu m preheated for 40min at 450 ℃ into the pure magnesium melt, and applying high-speed shearing at 6000rpm for 50s after every 1kg of zirconium powder is added. After 20kg of zirconium powder is completely added, the high-speed shearing at 8000rpm is continuously applied for 15min. Followed by applying 3000Hz sonication for 5min. Then pouring the mixture into a mold with the preheating temperature of 450 ℃, applying the pressure of 80MPa, keeping the pressure for 5min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-40Zr after solidification. The whole melt treatment process is operated under the protection of atmosphere. The grain size of active nucleation Zr in the prepared novel Mg-Zr high-efficiency grain refiner is 95 percent and is less than 5 mu m, wherein the grain size is 1 mu m-3 mu m at most, and the microstructure of the grain refiner is shown in figure 1.
7.2kg of the novel grain refiner is used for refining the melt grains of 300kg of Mg-Gd-Y alloy, and the large-scale complex casting of Mg-6.5Gd-3.5Y-0.6Zr is prepared by low-pressure casting, and the as-cast microstructure of the large-scale complex casting is shown in figure 2. After T6 treatment, the tensile property of the casting body at room temperature is measured: the tensile strength is more than 360MPa, and the elongation after fracture is more than 5%. The weight of the novel grain refiner is only 20 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 2
Placing preheated 5kg of pure magnesium at the bottom of a crucible, heating and smelting, after the temperature of a melt is raised to 680 ℃ and the pure magnesium is completely melted, adding 5kg of uniformly mixed zirconium/titanium infinite solid solution powder with the average grain size of 100 mu m preheated for 40min at 400 ℃ into the pure magnesium melt, wherein the mass ratio of zirconium to titanium is 3. After each 1kg of the infinite solid solution powder of zirconium/titanium was added, high-speed shearing at 5000rpm was applied for 30 seconds. After 5kg of zirconium/titanium infinite solid solution powder is completely added, high-speed shearing at 10000rpm is continuously applied for 10min. Followed by applying 3000Hz sonication for 5min. Then pouring the mixture into a die with the preheating temperature of 400 ℃, applying the pressure of 80MPa, maintaining the pressure for 10min, and preparing the novel efficient grain refiner for the Mg-50Ti/Zr rare earth magnesium alloy after solidification. The whole melt treatment process is operated under the protection of atmosphere. The particle size of active nucleation zirconium, titanium and zirconium/titanium infinite solid solution in the prepared novel Mg-50Ti/Zr high-efficiency grain refiner is 90% and is less than 5 mu m, and the microstructure of the novel Mg-50Ti/Zr high-efficiency grain refiner is shown in figure 3.
Example 3
Placing preheated 5kg of pure magnesium at the bottom of a crucible, heating and smelting, after the temperature of a melt is raised to 680 ℃ and the pure magnesium is completely melted, adding 5kg of uniformly mixed zirconium/titanium infinite solid solution powder with the average grain size of 20 mu m preheated for 30min at 350 ℃ into the pure magnesium melt, wherein the mass ratio of zirconium to titanium is 2. After each 1kg of infinite solid solution powder of zirconium/titanium was added, high-speed shearing at 6000rpm was applied for 30 seconds. After 5kg of zirconium/titanium infinite solid solution powder is completely added, high-speed shearing at 6000rpm is continuously applied for 15min. Followed by 3500Hz sonication for 15min. Then pouring the mixture into a mold with the preheating temperature of 500 ℃, applying the pressure of 80MPa, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the Mg-50Ti/Zr rare earth magnesium alloy after solidification. The whole melt treatment process is operated under the protection of inert atmosphere. The size of active nucleation titanium particles in the prepared novel Mg-50Ti/Zr high-efficiency grain refiner is 95 percent less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 500kg Mg-Gd-Y alloy, a large complex Mg-11Gd-1Y-0.6Ti/Zr casting is prepared by differential pressure casting, and the tensile property of a room temperature casting body is measured after T6 treatment: the tensile strength is above 386MPa, and the elongation after fracture is above 5.5%. The weight of the novel grain refiner is only 20 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 4
And (3) putting preheated 15kg of pure magnesium and pure zinc at the bottom of a crucible, heating and smelting, controlling the temperature at 450 ℃, and preserving the temperature for 60min to obtain semi-solid slurry with nominal components of Mg-20 Zn. Adding 15kg of uniformly mixed zirconium/titanium infinite solid solution powder with the average grain size of 20 mu m preheated for 40min at 450 ℃ into the Mg-Zn alloy semi-solid slurry, wherein the mass ratio of zirconium to titanium is 3. Meanwhile, high-speed shearing treatment is carried out on the middle part of the semi-solid slurry, and after 1.5kg of zirconium/titanium powder is added, high-speed shearing at 8000rpm is carried out for 60s. After 15kg of the infinite solid solution powder of zirconium/titanium is added, high-speed shearing at 8000rpm is continuously applied for 10min. Then the temperature of the melt is raised to 710-720 ℃, high-speed shearing at 8000rpm is continuously applied for 10min, and then ultrasonic treatment at 4000Hz is applied for 10min. And then pouring the melt into a die with the preheating temperature of 400 ℃, applying 100MPa pressure, keeping the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-10Zn-50Ti/Zr after solidification. The particle size of the active nucleation zirconium titanium infinite solid solution in the prepared novel rare earth Mg-Zn-Ti/Zr high-efficiency grain refiner is 90 percent and is less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 1000kg Mg-Gd-Y alloy, and semi-continuous casting is carried out to prepare Mg-9Gd-3Y-2Zn-0.6Ti/Zr semi-continuous cast ingot with the diameter of 450mm, the grains of the core part and the edge part of the ingot are fine and uniform, and the average grain size is about 40-50 mu m. After extrusion with an extrusion ratio of 9 and T5 heat treatment, the mechanical properties of the bar at room temperature are measured as follows: the tensile strength is more than 490MPa, and the elongation after fracture is more than 6%. The weight of the novel grain refiner is only 20 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 5
And (3) putting preheated 20kg of pure magnesium and pure zinc at the bottom of a crucible, heating and smelting, controlling the temperature at 460 ℃, and preserving the heat for 60min to obtain semi-solid slurry with nominal components of Mg-20 Zn. 10kg of zirconium powder having an average grain size of 10 μm preheated at 400 ℃ for 30min was added to the Mg-Zn alloy semi-solid slurry. Meanwhile, high-speed shearing treatment is carried out on the middle part of the semi-solid slurry, and after 1kg of zirconium powder is added, high-speed shearing at 6000rpm is carried out for 60s. After 10kg of zirconium powder is completely added, high-speed shearing at 6000rpm is continuously applied for 10min. The melt temperature was then raised to 680 ℃ and the high shear at 6000rpm was continued for 5min and the ultrasonic treatment at 4000Hz for 5min. And then pouring the melt into a die with the preheating temperature of 400 ℃, applying the pressure of 100MPa, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-13.3Zn-33Zr after solidification. The particle size of the active nucleation zirconium titanium infinite solid solution in the prepared novel rare earth Mg-Zn-Zr high-efficiency grain refiner is 98 percent and is less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 800kg Mg-Gd-Y alloy, and semi-continuous casting is carried out to prepare Mg-13.5Gd-1.5Y-1.2Zn-0.55Zr semi-continuous cast ingots with the diameter of 420mm, the grains of the core part and the edge part of the semi-continuous cast ingots are fine and uniform, and the average grain size is about 35 to 50 mu m. After extrusion with an extrusion ratio of 9 and T5 heat treatment, the mechanical properties of the bar at room temperature are measured as follows: the tensile strength is more than 510MPa, and the elongation after fracture is more than 6.5 percent. The weight of the novel grain refiner is only 25 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 6
And (3) putting 30kg of preheated pure magnesium at the bottom of a crucible, heating and smelting, and adding 20kg of titanium powder with the average grain size of 50 microns, preheated for 60min at 350 ℃, into the pure magnesium melt after the pure magnesium is completely molten when the melt temperature is raised to 680 ℃. After each 2kg of titanium powder was added, high-speed shearing was applied at 8000rpm for 60 seconds. After 20kg of titanium powder is completely added, high-speed shearing at 8000rpm is continuously applied for 20min. Followed by applying 3000Hz sonication for 10min. Then pouring the mixture into a metal die with the preheating temperature of 450 ℃, applying the pressure of 100MPa, keeping the pressure for 10min, and obtaining the efficient grain refiner for the novel Mg-40Ti rare earth magnesium alloy after solidification. The whole melt treatment process is operated under the protection of nitrogen inert atmosphere. The grain size of active nucleation titanium in the prepared novel Mg-Ti efficient grain refiner is 92 percent less than 5 mu m.
Example 7
Putting preheated 25kg of pure magnesium at the bottom of a crucible, heating and smelting, after the temperature of a melt rises to completely melt the pure magnesium, adding 25kg of zirconium powder with the average grain size of 10 mu m preheated for 45min at 350 ℃ into the pure magnesium melt, and shearing at 6000rpm for 60s after adding 1kg of zirconium powder. After 25kg of zirconium powder is completely added, high-speed shearing at 6000rpm is continuously applied for 20min. Followed by applying 3000Hz sonication for 10min. Then pouring the mixture into a die with the preheating temperature of 400 ℃, applying the pressure of 120MPa, maintaining the pressure for 8min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-50Zr after solidification. The whole melt treatment process is operated under the protection of atmosphere. The grain size of active nucleation Zr in the prepared novel Mg-Zr high-efficiency grain refiner is 95 percent and is less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 800kg Mg-Gd-Y alloy, and semi-continuous casting is carried out to prepare Mg-8.5Gd-3.5Y-1.5Zn-0.55Zr semi-continuous cast ingots with the diameter of 450mm, the grains of the core part and the edge part of the semi-continuous cast ingots are fine and uniform, and the average grain size is about 35 to 50 mu m. After multidirectional cogging forging and T5 heat treatment, the room-temperature mechanical properties of the forging stock with the diameter of more than 1000mm in all directions are measured: the tensile strength is more than 440MPa, and the elongation after fracture is more than 6%. The weight of the novel grain refiner is 25 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 8
And (3) putting 20kg of preheated pure magnesium and pure zinc at the bottom of a crucible, heating and smelting, controlling the temperature at 550 ℃, and preserving the heat for 60min to obtain semi-solid slurry with nominal components of Mg-30 Cu. 20kg of zirconium powder having an average grain size of 100 μm preheated at 450 ℃ for 30min was added to the Mg-Cu alloy semi-solid slurry. Meanwhile, high-speed shearing treatment is carried out on the middle part of the semi-solid slurry, and after 2kg of zirconium powder is added, high-speed shearing at 8000rpm is carried out for 60s. After 20kg of zirconium powder is added, high-speed shearing at 8000rpm is continuously applied for 10min. The melt temperature was then raised to 680 ℃ and further shearing at 8000rpm for 10min and sonication at 4000Hz for 10min was applied. And then pouring the melt into a mold with the preheating temperature of 450 ℃, applying 100MPa pressure, keeping the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-15Cu-50Zr after solidification. The particle size of the active nucleation zirconium-titanium infinite solid solution in the prepared novel Mg-Cu-Zr high-efficiency grain refiner is 95 percent and is less than 5 mu m.
The novel grain refiner is used for melt grain refining treatment of 1000kg Mg-Gd-Y alloy, and semi-continuous casting is carried out to prepare Mg-9Gd-3Y-1.5Cu-0.55Zr semi-continuous cast ingots with the diameter of 450mm, the grains of the core part and the edge part of the semi-continuous cast ingots are fine and uniform, and the average grain size is about 40 to 60 mu m. After extrusion with an extrusion ratio of 9 and T5 heat treatment, the mechanical properties of the bar at room temperature are measured as follows: tensile strength of 520MPa or more and elongation after fracture of 6% or more. The weight of the novel grain refiner is only 30 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 9
And (3) putting preheated 15kg of pure magnesium and pure zinc at the bottom of a crucible, heating and smelting, controlling the temperature at 600 ℃, and keeping the temperature for 60min to obtain semi-solid slurry with nominal components of Mg-20 Ni. 15kg of zirconium powder having an average grain size of 100 μm preheated for 60min at 450 ℃ was added to the Mg-Ni alloy semi-solid slurry. Meanwhile, high-speed shearing treatment is carried out on the middle part of the semi-solid slurry, and after 1.5kg of zirconium powder is added, high-speed shearing at 6000rpm is carried out for 30s. After 15kg of zirconium powder is completely added, high-speed shearing at 6000rpm is continuously applied for 15min. The melt temperature was then raised to 680 ℃ and the high shear of 6000rpm was continued for 5min and sonication at 3000Hz for 10min. And then pouring the melt into a mold with the preheating temperature of 450 ℃, applying 80MPa pressure, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-10Ni-50Zr after solidification. The grain size of the active nucleation zirconium titanium infinite solid solution in the prepared novel Mg-Ni-Zr high-efficiency grain refiner is 90 percent and is less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 800kg Mg-Gd-Y alloy, and the Mg-8.5Gd-3.5Y-1.2Ni-0.5Zr semi-continuous cast ingot with the diameter of 420mm is prepared by semi-continuous casting, the grains of the core part and the edge part of the semi-continuous cast ingot are fine and uniform, and the average grain size is about 30 to 60 mu m. After extrusion with an extrusion ratio of 9 and T5 heat treatment, the mechanical properties of the bar at room temperature are measured as follows: the tensile strength is more than 510MPa, and the elongation after fracture is more than 6%. The weight of the novel grain refiner is only 25 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Example 10
Putting preheated 15kg of pure magnesium, pure zinc and pure copper into the bottom of a crucible, heating and smelting, controlling the temperature at 470 ℃, and preserving the heat for 60min to obtain semi-solid slurry with nominal components of Mg-20Zn-10 Cu. 10kg of zirconium powder and titanium powder having an average grain size of 50 μm preheated for 60min at 450 ℃ were added to the Mg-Zn-Cu alloy semi-solid slurry. Meanwhile, high-speed shearing treatment is carried out on the middle part of the semi-solid slurry, and after 1kg of titanium/zirconium powder is added, high-speed shearing at 8000rpm is carried out for 60s. After 10kg of zirconium powder and titanium powder are added, high-speed shearing at 8000rpm is continuously carried out for 10min. The melt temperature was then raised to 680 ℃ and further shearing at 8000rpm for 10min and sonication at 4000Hz for 10min was applied. And then pouring the melt into a mold with the preheating temperature of 500 ℃, applying the pressure of 100MPa, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-10Zn-5Cu-40Ti/Zr after solidification. The particle size of the active nucleation zirconium-titanium infinite solid solution in the prepared novel Mg-Zn-Cu-Ti/Zr high-efficiency grain refiner is 95 percent and is less than 5 mu m.
The novel grain refiner is used for refining the melt grains of 1000kg Mg-Gd alloy, and semi-continuous casting is carried out to prepare Mg-13.5Gd-1Zn-0.5Cu-0.5Ti/Zr semi-continuous cast ingots with the diameter of 450mm, the grains of the core part and the edge part of the semi-continuous cast ingots are fine and uniform, and the average grain size is about 20 to 50 mu m. After extrusion with an extrusion ratio of 9 and T5 heat treatment, the mechanical properties of the bar at room temperature are measured as follows: the tensile strength is more than 550MPa, and the elongation after fracture is more than 6%. The weight of the novel grain refiner is only 25 percent of that of the Mg-30Zr refiner prepared by the traditional molten salt method.
Comparative example
Comparative example 1
Mg-30Zr prepared by a traditional molten salt method is used as a refiner 36kg, is used for refining melt grains of 300kg Mg-Gd-Y alloy, and is treated by T6 to obtain a large complex casting of Mg-6.5Gd-3.5Y-0.6Zr, wherein the large complex casting is obtained by low-pressure casting, and the tensile property of the casting body at room temperature is measured: tensile strength of 310-330 MPa, and elongation after fracture of 3% -4.5%. The microstructure of the as-cast Mg-6.5Gd-3.5Y-0.6Zr alloy treated with the conventional Mg-30Zr refiner is shown in FIG. 4.
Comparative example 2
The Mg-30Zr prepared by the traditional molten salt method is used as a refiner 88kg, is used for refining the melt crystal grains of 800kg Mg-Gd-Y alloy, and is used for preparing large-scale cast ingots through semi-continuous casting, and the core part structure and the edge part structure of the prepared Mg-8.5Gd-3.5Y-1.5Zn-0.55Zr with the diameter of 450mm have fine and uniform inner and outer crystal grains, and the average crystal grain size is about 80-100 mu m. After multidirectional cogging forging and T5 heat treatment, the forging stock with the diameter of more than 1000mm has the sampling tensile strength of 350MPa to 370MPa and the elongation after fracture of 3 percent to 5 percent. The Mg-30Zr refining agent is added according to more than 5 percent of the Zr content of the alloy.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are not particularly limited to the specific examples described herein.
Claims (10)
1. The preparation method of the efficient grain refiner for the rare earth magnesium alloy is characterized by comprising the following steps:
adding the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt or a semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic waves, and solidifying to obtain the grain refiner for the rare earth magnesium alloy.
2. The preparation method of the efficient grain refiner for rare earth magnesium alloy according to claim 1, wherein when the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into a pure magnesium melt to prepare the grain refiner for rare earth magnesium alloy, the preparation method comprises the following steps:
heating pure magnesium to a complete molten state to obtain a pure magnesium melt; then adding the weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into the pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain the magnesium melt with uniformly distributed titanium-containing element or zirconium-containing element or titanium/zirconium-containing element; and then pouring the melt into a mold, solidifying under the action of pressure, preparing the grain refiner for the rare earth magnesium alloy after complete solidification, and carrying out the whole preparation process under the protection of a vacuum environment or inert atmosphere.
3. The method for preparing the efficient grain refiner for rare earth magnesium alloy according to claim 2, wherein the preheating temperature of the titanium powder, the zirconium powder or the uniformly mixed titanium/zirconium powder is 300-600 ℃, and the preheating time is 30-90 min; and/or
The specific adding mode of the powder is as follows: dividing the added powder into n parts, wherein n is more than or equal to 5 and less than or equal to 30, applying high-speed shearing for 30-90 s after every 1 part of the powder is added, the rotating speed of a rotor is 5000-20000 rpm, continuously applying high-speed shearing for 10-60 min after the powder is completely added, and then applying ultrasonic treatment, wherein the technological parameter of the ultrasonic treatment is 2000-5000 Hz, and the time of the ultrasonic treatment is 2-15 min; and/or
The solidification process comprises the steps of pouring magnesium melt containing titanium or zirconium or titanium/zirconium into a metal mold with the preheating temperature of 300-600 ℃, applying the pressure of 60-150 MPa, and keeping the pressure for 5-30 min.
4. The method for preparing the efficient grain refiner for rare earth magnesium alloy according to claim 2, wherein the efficient grain refiner for rare earth magnesium alloy comprises Mg- (30-70) Ti or Mg- (30-70) Zr or Mg- (30-70) (Ti/Zr) (wt.%).
5. The preparation method of the efficient grain refiner for rare earth magnesium alloy according to claim 1, wherein the preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is added into the semi-solid molten magnesium alloy, and when the grain refiner for rare earth magnesium alloy is prepared, the preparation method comprises the following steps:
heating pure magnesium alloy to a semi-solid state, adding weighed and fully preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a completely molten state after all the powder is added, applying high-speed shearing and ultrasonic treatment to obtain a magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated die, solidifying under the action of pressure, preparing a grain refiner for rare earth magnesium alloy after complete solidification, and performing the whole preparation process under the protection of a vacuum environment or an inert atmosphere.
6. The method for preparing the efficient grain refiner for rare earth magnesium alloy according to claim 5, wherein the preheating temperature of the titanium powder, the zirconium powder or the uniformly mixed titanium/zirconium powder is 300-600 ℃, and the preheating time is 30-90 min; and/or
The specific adding mode of the powder is as follows: dividing the added powder into n parts, wherein n is more than or equal to 5 and less than or equal to 30, and applying high-speed shearing for 30-120 s after every 1 part of the powder is added, and the rotating speed of a rotor is 6000-20000 rpm; after the powder is completely added, continuously applying high-speed shearing at 6000 rpm-20000 rpm for 5 min-60 min; heating the magnesium alloy to a complete molten state, and applying high-speed shearing and ultrasonic treatment, wherein the rotating speed of a high-speed shearing rotor is 6000-20000 rpm, and the treatment time is 5-60 min; then ultrasonic treatment is carried out, the technological parameter of the ultrasonic treatment is 3000 Hz-5000 Hz, and the ultrasonic treatment time is 5 min-30 min; and/or
The solidification process is to pour magnesium melt containing titanium or zirconium or titanium/zirconium into a metal mold with the preheating temperature of 300-600 ℃, apply the pressure of 80-150 MPa, and maintain the pressure for 5-30 min.
7. The method for preparing the efficient grain refiner for rare earth magnesium alloy according to claim 5, wherein the magnesium alloy in the semi-solid state is Mg-TM system, wherein TM is one or a mixture of Zn, cu and Ni; the efficient grain refiner for the rare earth magnesium alloy comprises the components of Mg- (10-30) TM- (30-60) Ti, mg- (10-30) TM- (30-60) Zr or Mg- (10-30) TM- (30-60) (Ti/Zr) (wt.%).
8. The method for preparing the efficient grain refiner for rare earth magnesium alloy according to claim 1, wherein the average grain diameter of the titanium powder or the zirconium powder or the uniformly mixed titanium/zirconium powder is 0.001-1000 μm, preferably 0.01-100 μm, and more preferably 0.1-20 μm.
9. An efficient grain refiner for rare earth magnesium alloy, which is characterized by being prepared by the preparation method of the efficient grain refiner for rare earth magnesium alloy according to any one of claims 1 to 8, wherein the grain refiner for rare earth magnesium alloy has the active nucleation Ti or Zr or (Ti/Zr) particle size of 85-99.9% and is smaller than 5 μm.
10. The use method of the efficient grain refiner for the rare earth magnesium alloy is characterized by comprising the following steps:
weighing raw materials with corresponding weight according to the components and the mass percent of the magnesium alloy, adding the grain refiner of claim 9 after the raw materials are completely melted and skimmed, fishing out the bottom and stirring after the raw materials are completely melted, and then refining; and after refining, removing slag, standing, and using the prepared melt for preparing rare earth magnesium alloy castings or rare earth magnesium alloy semi-continuous casting ingots.
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