CN115652155B - Grain refiner for rare earth magnesium alloy, preparation method and use method thereof - Google Patents
Grain refiner for rare earth magnesium alloy, preparation method and use method thereof Download PDFInfo
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- CN115652155B CN115652155B CN202211351355.6A CN202211351355A CN115652155B CN 115652155 B CN115652155 B CN 115652155B CN 202211351355 A CN202211351355 A CN 202211351355A CN 115652155 B CN115652155 B CN 115652155B
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 109
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 102
- 239000011777 magnesium Substances 0.000 claims abstract description 58
- 238000010008 shearing Methods 0.000 claims abstract description 58
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000007670 refining Methods 0.000 claims abstract description 25
- 230000006911 nucleation Effects 0.000 claims abstract description 20
- 238000010899 nucleation Methods 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims description 144
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 102
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 92
- 229910052726 zirconium Inorganic materials 0.000 claims description 61
- 239000007787 solid Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims description 28
- 239000000155 melt Substances 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 238000007711 solidification Methods 0.000 claims description 20
- 230000008023 solidification Effects 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000010128 melt processing Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000006104 solid solution Substances 0.000 description 17
- 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
- 238000009749 continuous casting Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 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
- 238000005242 forging Methods 0.000 description 4
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000009036 growth inhibition Effects 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
- 230000001427 coherent effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 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
- 229910000748 Gd alloy Inorganic materials 0.000 description 1
- 229910019086 Mg-Cu Inorganic materials 0.000 description 1
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 229910007995 ZrF2 Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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 use method thereof. The high-speed shearing melt processing method and ultrasonic processing adopted by the invention can uniformly distribute Ti, zr or Ti/Zr powder with high mass fraction in the magnesium matrix, and compared with the traditional method, the method improves the content of Ti, zr or Ti/Zr in the grain refiner, ensures that Ti, zr or Ti/Zr is uniformly distributed, reduces the agglomeration and growth of nucleation particles, and improves the utilization rate and refining effect of the refiner.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy grain refinement, and particularly relates to a high-efficiency 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 heat resistance, high strength, high toughness and the like, has wide application prospect in parts such as an aircraft cabin body, a satellite structural member, an airship frame, an engine bonnet, an engine cylinder body, a gearbox shell and the like, and is highly concerned. However, under the condition of large smelting amount of engineering application, natural contradiction exists between rare earth magnesium alloy melt purification and grain refinement. The traditional magnesium-zirconium intermediate alloy form is adopted for refining the magnesium alloy, so that 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 serving as a light material on an aircraft is prevented.
Zr is the most effective grain refiner for magnesium alloys other than Al, mn, si, etc. Zr can reduce the fierce tendency and improve the toughness of the alloy. Zr in magnesium alloys is typically added in the form of mg—zr master alloys. The intermediate alloy is usually produced by a method of reducing K 2ZrF2 by Mg, and the prepared Mg-Zr intermediate alloy 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 and poor refining effect, and the spontaneous settlement of Zr ensures that a plurality of times of Zr is added in the production to obtain enough Zr amount, and the actual ingot casting only needs less than 1 percent of Zr. And the Mg-Zr intermediate alloy prepared by the traditional method also contains more impurities, a large amount of solvent is needed to settle the Mg-Zr intermediate alloy, and a large amount of added 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, so that the components are supercooled, the growth of crystal grains is inhibited, and the grain refinement capability is very strong. The Ti element has great potential as the efficient 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 hexagons, the lattice constant of alpha-Ti is similar to that of Mg, and the alpha-Ti has good coherent relation with Mg, and can become a high-quality heterogeneous nucleation core of Mg from the aspect of crystallography. However, ti is difficult to be added into magnesium alloy alone, the melting point of the Ti is even larger than that of Mg, and the loss amount of directly adding pure Ti is large and the process is complex. Therefore, the Ti-containing master alloy can have a lower melting point than pure Ti and can improve the yield of the alloying elements. However, no effective method is available at present to realize the addition of Ti, which results in limited grain refinement effect of the rare earth magnesium alloy. Therefore, there is a need to develop more efficient grain refiner manufacturing methods to improve the performance level of magnesium alloy materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor performs intensive researches and provides a high-efficiency grain refiner for rare earth magnesium alloy, a preparation method and a use method thereof, wherein preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder is added into pure magnesium melt or semi-solid molten magnesium alloy, and high-speed shearing and ultrasonic means are applied, so that the novel high-efficiency grain refiner for rare earth magnesium alloy containing high-content and more efficient active nucleated zirconium particles, titanium particles or titanium/zirconium infinite solid solution particles is prepared.
The technical scheme provided by the invention is as follows:
In a first aspect, a method for preparing an efficient grain refiner for rare earth magnesium alloys comprises: adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into pure magnesium melt or semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic treatment, and solidifying to obtain the 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 melting state to obtain pure magnesium melt; then adding the well weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain a magnesium melt containing titanium element or zirconium element or uniformly distributed titanium/zirconium element; then pouring the melt into a mould, solidifying under the action of pressure, and preparing the grain refiner for the rare earth magnesium alloy after the melt is completely solidified, wherein the whole preparation process is carried out under the protection of a vacuum environment or an inert atmosphere;
The preparation method specifically comprises the steps of adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into the semi-solid molten magnesium alloy, and preparing the grain refiner for the rare earth magnesium alloy: 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 the semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a complete melting state after the powder is fully added, applying high-speed shearing and ultrasonic treatment to obtain magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated mold, solidifying under the action of pressure, and preparing the grain refiner for the rare earth magnesium alloy after complete solidification, wherein the whole preparation process is carried out under the protection of vacuum environment or inert atmosphere.
According to a second aspect, the efficient grain refiner for the rare earth magnesium alloy is prepared according to the preparation method of the efficient grain refiner for the rare earth magnesium alloy in the first aspect, wherein the active nucleation Ti or Zr or (Ti/Zr) particle size in the grain refiner for the rare earth magnesium alloy is 85% -99.9% less than 5 mu m.
In a third aspect, a method for using a high-efficiency grain refiner for rare earth magnesium alloy is characterized by comprising the following steps: weighing raw materials with corresponding weight according to the magnesium alloy components and the mass percentages thereof, 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; after refining, removing slag, standing, and using the prepared melt for preparing rare earth magnesium alloy castings or semi-continuous ingots of rare earth magnesium alloy castings.
The efficient grain refiner for the rare earth magnesium alloy, the preparation method and the use method thereof have 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 elements with higher content, and the mass fraction reaches 30-70%. And has a higher content of fine and uniform nucleation particles, with a Ti or Zr or (Ti/Zr) particle size of 85% -99.9% being less than 5 μm.
2. The growth inhibition factor of Ti is 59500, the lattice constant of Ti is similar to that of Mg, the Ti has good coherent relation with Mg, and Ti is a very efficient grain refiner. The Mg-Ti or Mg-TM-Ti and Mg-Ti/Zr or Mg-TM-Ti/Zr high-efficiency grain refiner contains a large number of tiny active nucleation Ti particles or Ti/Zr particles, and the growth inhibition factors of Ti and Ti/Zr are more than 1500 times of Zr, so that the grain refiner has more excellent grain refining capability.
3. Because Ti and Zr can form 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 basic crystal surface of the magnesium matrix is reduced, the degree of lattice matching with the magnesium matrix is improved, the supercooling of components is increased, the matrix and the second phase can be obviously refined, and the addition amount of Ti/Zr can reach the maximum addition amount of Zr.
4. The high-speed shearing melt processing method adopted by the invention can uniformly distribute Ti, zr or Ti/Zr powder with high mass fraction in the magnesium matrix, and compared with the traditional method, the method improves the Ti, zr or Ti/Zr content in the grain refiner. The uniform distribution of Ti, zr or Ti/Zr can be further improved by high-speed shearing treatment, the agglomeration growth of nucleation particles is reduced, and the utilization rate and the refining effect of the refiner are improved. In addition, the grain size of Ti, zr or Ti/Zr can be further refined by high-speed shearing in the melt treatment, large particles are crushed into micrometer or even nanometer level, 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 state region, and the ultrasonic treatment is applied to the liquid phase region, so that not only can the dispersion effect be further improved, but also a small amount of gas introduced in the high-speed shearing can be discharged. Pressure is applied during the solidification process, so that the internal defects of the grain refiner are further reduced. The defects of compact structure, air holes, shrinkage porosity, sand holes, refined particle agglomeration and the like of the prepared grain refiner are greatly reduced by high-speed shearing treatment, ultrasonic treatment and pressure solidification. The high-quality grain refiner can be well inherited into 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 method has good component uniformity, and the effective Ti, zr or uniformly mixed Ti/Zr infinite solid solution particles are more, so that the consumption of the grain refiner required to be added is reduced, and the manufacturing cost can be further reduced.
7. The Mg-Ti-Zr high-efficiency grain refiner prepared by the method has low inclusion content, greatly improves the purity of the rare earth magnesium alloy melt, reduces the time required for standing and deslagging of the melt, can obviously improve the purification effect of the melt, and has clean and tidy interface.
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, has slow sedimentation velocity in the standing process, effectively solves the problems of sedimentation and refinement decay of the original grain refiner, and has fine grains and uniform cast structure at each position of castings or ingots prepared by the novel grain refiner.
9. The smelting process of the rare earth magnesium alloy needs to add a large amount of flux, namely the covering agent and the refining agent for deslagging, and the refining agent only needs to be added once, so that the defect of inclusion of the flux of castings and cast ingots is greatly reduced.
Drawings
FIG. 1 is a microstructure of a novel Mg-40Zr 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 a microstructure of a novel Mg-50Ti/Zr grain refiner of Mg-50 in example 2;
FIG. 4 is an as-cast Mg-6.5Gd-3.5Y-0.6Zr alloy microstructure of comparative example 1 treated with a conventional Mg-30Zr refiner.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used 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. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to a first aspect of the invention, there is provided a method for preparing a high-efficiency grain refiner for rare earth magnesium alloy, comprising the steps of: adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into pure magnesium melt or semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic treatment, and solidifying to obtain the grain refiner for rare earth magnesium alloy. The average particle diameter of the titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is 0.001 μm to 1000. Mu.m, preferably 0.01 μm to 100. Mu.m, more preferably 0.1 μm to 20. Mu.m.
In the invention, when preheated titanium powder or zirconium powder or evenly mixed titanium/zirconium powder is added into 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 melting state to obtain pure magnesium melt; then adding the well weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain a magnesium melt containing titanium element or zirconium element or uniformly distributed titanium/zirconium element; and then pouring the melt into a mould, solidifying under the action of pressure, and obtaining the grain refiner for the rare earth magnesium alloy after complete solidification, wherein the whole preparation process is carried out under the protection of a vacuum environment or an inert atmosphere.
In this embodiment, the preheating temperature of the titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder is 300 ℃ to 600 ℃ and the preheating time is 30min to 90min.
The concrete 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 adding 1 part, and continuously applying high-speed shearing for 10-60 min after the powder is completely added, and then applying ultrasonic treatment, wherein the ultrasonic treatment process parameter is 2000-5000 Hz, and the ultrasonic treatment time is 2-15 min.
The solidification process is to pour the magnesium melt containing titanium or zirconium or titanium/zirconium element into a metal mold with the preheating temperature of 300-600 ℃, and apply the pressure of 60-150 MPa, and the pressure is maintained for 5-30 min.
The components of the prepared high-efficiency grain refiner for the 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 preheated titanium powder or zirconium powder or evenly mixed titanium/zirconium powder is added into semi-solid molten 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 the semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a complete melting state after the powder is fully added, applying high-speed shearing and ultrasonic treatment to obtain magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated mold, solidifying under the action of pressure, and preparing the grain refiner for the rare earth magnesium alloy after complete solidification, wherein the whole preparation process is carried out under the protection of vacuum environment or 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 concrete 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, wherein the rotating speed of a rotor is 6000-20000 rpm; after the powder is fully 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, 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 applied, 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 the magnesium melt containing titanium or zirconium or titanium/zirconium element into a metal mold with the preheating temperature of 300-600 ℃, and apply 80-150 MPa pressure, and keep the pressure for 5-30 min.
The semi-solid state magnesium alloy is Mg-TM system, wherein TM is one or more of Zn, cu and Ni elements; the components of the high-efficiency grain refiner for the rare earth magnesium alloy are 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 high-efficiency 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 high-efficiency grain refiner for rare earth magnesium alloy comprises Mg- (20-35) TM- (33-50) Ti or Mg- (20-35) TM- (33-50) Zr or Mg- (20-35) TM- (33-50) (Ti/Zr) (wt.%), wherein TM is Zn, cu and Ni. 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-15Cu-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, there is provided a high-efficiency grain refiner for rare earth magnesium alloy, prepared according to the preparation method of the high-efficiency grain refiner for rare earth magnesium alloy of the first aspect, wherein the grain refiner for rare earth magnesium alloy has an active nucleation Ti or Zr or (Ti/Zr) particle size of 85% -99.9% less than 5 μm.
According to a third aspect of the present invention, there is provided a method of using a high-efficiency grain refiner for rare earth magnesium alloys, comprising: weighing raw materials with corresponding weight according to the magnesium alloy components and the mass percentage thereof, adding the grain refiner 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; after refining, removing slag, standing, and using the prepared melt for preparing rare earth magnesium alloy castings or semi-continuous ingots of rare earth magnesium alloy castings.
Examples
Example 1
And placing 30kg of preheated pure magnesium into 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 at 450 ℃ for 40min into the pure magnesium melt, and applying high-speed shearing at 6000rpm for 50s after adding 1kg of zirconium powder. After 20kg of zirconium powder was added in its entirety, high-speed shearing at 8000rpm was continued for 15min. Followed by 5min of sonication at 3000 Hz. And then pouring the mixture into a die with the preheating temperature of 450 ℃, applying 80MPa pressure, maintaining the pressure for 5 minutes, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-40Zr after solidification is completed. The whole melt processing process is operated under atmosphere protection. The active nucleation Zr particle size in the prepared novel Mg-Zr high-efficiency grain refiner is less than 5 mu m, wherein the maximum size is 1 mu m-3 mu m, and the microstructure is shown in figure 1.
7.2Kg of the novel grain refiner is used for refining melt grains of 300kg of Mg-Gd-Y alloy, and the cast microstructure of the Mg-6.5Gd-3.5Y-0.6Zr large complex casting prepared by low-pressure casting is shown in figure 2. After T6 treatment, the tensile property of the room temperature casting body is measured: tensile strength is more than 360MPa, and elongation after breaking 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
And placing 5kg of preheated pure magnesium into the bottom of a crucible for heating and smelting, and after the temperature of the 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 at 400 ℃ for 40min into the pure magnesium melt, wherein the mass ratio of zirconium to titanium is 3:2. After each addition of 1kg of zirconium/titanium infinite solid solution powder, high-speed shearing at 5000rpm was applied for 30 seconds. After 5kg of zirconium/titanium infinite solid solution powder was added all, high-speed shearing at 10000rpm was continued for 10min. Followed by 5min of sonication at 3000 Hz. And then pouring the mixture into a die with the preheating temperature of 400 ℃, applying 80MPa pressure, maintaining the pressure for 10 minutes, and obtaining the efficient grain refiner for the Mg-50Ti/Zr novel rare earth magnesium alloy after solidification is completed. The whole melt processing process is operated under atmosphere protection. The particle size of 90% of active nucleation zirconium, titanium and zirconium/titanium infinite solid solution in the novel Mg-50Ti/Zr high-efficiency grain refiner is smaller than 5 mu m, and the microstructure is shown in figure 3.
Example 3
And placing 5kg of preheated pure magnesium into the bottom of a crucible for heating and smelting, preheating at 350 ℃ for 30min after the pure magnesium is completely melted at 680 ℃, and adding 5kg of uniformly mixed zirconium/titanium infinite solid solution powder with the average grain size of 20 mu m into the pure magnesium melt, wherein the mass ratio of zirconium to titanium is 2:3. After each addition of 1kg of zirconium/titanium infinite solid solution powder, high-speed shearing at 6000rpm was applied for 30s. After 5kg of zirconium/titanium infinite solid solution powder was added all, high-speed shearing at 6000rpm was continued for 15min. Followed by ultrasonic treatment at 3500Hz for 15min. And then pouring the mixture into a die with the preheating temperature of 500 ℃, applying 80MPa pressure, maintaining the pressure for 10 minutes, and obtaining the efficient grain refiner for the Mg-50Ti/Zr novel rare earth magnesium alloy after solidification is completed. The whole melt treatment process is operated under the protection of inert atmosphere. The size of the active nucleation titanium particles in the novel Mg-50Ti/Zr novel high-efficiency grain refiner is less than 5 mu m at 95%.
The novel grain refiner is used for refining melt grains of 500kg of Mg-Gd-Y alloy, a large-scale complex casting of Mg-11Gd-1Y-0.6Ti/Zr is prepared through differential pressure casting, and the tensile property of a room-temperature casting body is measured after T6 treatment: the tensile strength is 386MPa or more, and the elongation after break is 5.5% or more. 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) placing 15kg of preheated pure magnesium and pure zinc into the bottom of a crucible, heating and smelting, controlling the temperature at 450 ℃, and preserving the heat for 60 minutes to prepare the semi-solid slurry with the name and meaning of Mg-20 Zn. 15kg of uniformly mixed zirconium/titanium infinite solid solution powder with the average grain size of 20 mu m preheated at 450 ℃ for 40min is added into the Mg-Zn alloy semi-solid slurry, wherein the mass ratio of zirconium to titanium is 3:2. At the same time, a high-speed shearing treatment was applied to the middle of the semi-solid slurry, and after each 1.5kg of zirconium/titanium powder was added, a high-speed shearing at 8000rpm was applied for 60 seconds. After 15kg of zirconium/titanium infinite solid solution powder is fully 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 4000Hz ultrasonic treatment is applied for 10min. And pouring the melt into a die with the preheating temperature of 400 ℃, applying 100MPa pressure, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-10Zn-50Ti/Zr after solidification is completed. The particle size of the active nucleation zirconium titanium infinite solid solution in the novel rare earth Mg-Zn-Ti/Zr novel high-efficiency grain refiner is 90 percent smaller than 5 mu m.
The novel grain refiner is used for refining melt grains of 1000kg of Mg-Gd-Y alloy, and the Mg-9Gd-3Y-2Zn-0.6Ti/Zr semicontinuous cast ingot with the diameter of 450mm is prepared by semicontinuous casting, and the grains of the structures at the core part and the edge part are fine and uniform, and the average grain size is about 40-50 mu m. After extrusion with the extrusion ratio of 9, after T5 heat treatment, the mechanical properties of the bar at room temperature are measured: the tensile strength is above 490MPa, and the elongation after breaking is above 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 placing 20kg of preheated pure magnesium and pure zinc into the bottom of a crucible, heating and smelting, controlling the temperature at 460 ℃, and preserving the heat for 60 minutes to prepare the semi-solid slurry with the name 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. At the same time, a high-speed shearing treatment was applied to the middle of the semi-solid slurry, and after each 1kg of zirconium powder was added, a high-speed shearing at 6000rpm was applied for 60 seconds. After 10kg of zirconium powder was added in its entirety, high-speed shearing at 6000rpm was continued for 10min. The melt temperature was then raised to 680℃and high shear at 6000rpm was continued for 5min and sonication at 4000Hz was continued for 5min. And then pouring the melt into a die with the preheating temperature of 400 ℃, applying 100MPa pressure, 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 is completed. The particle size of the active nucleation zirconium titanium infinite solid solution in the novel rare earth Mg-Zn-Zr novel high-efficiency grain refiner is 98 percent smaller than 5 mu m.
The novel grain refiner is used for refining melt grains of 800kg of Mg-Gd-Y alloy, and the semi-continuous casting ingot of Mg-13.5Gd-1.5Y-1.2Zn-0.55Zr with the diameter of 420mm is prepared by semi-continuous casting, and the grains of the core and the edge tissues are fine and uniform, and the average grain size is about 35 mu m to 50 mu m. After extrusion with the extrusion ratio of 9, after T5 heat treatment, the mechanical properties of the bar at room temperature are measured: the tensile strength is above 510MPa, and the elongation after breaking is above 6.5%. 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 placing 30kg of preheated pure magnesium into the bottom of a crucible, heating and smelting, and adding 20kg of titanium powder with the average grain size of 50 mu m preheated at 350 ℃ for 60min into the pure magnesium melt after the temperature of the melt is increased to 680 ℃ and the pure magnesium is completely melted. After each addition of 2kg of titanium powder, high-speed shearing at 8000rpm was applied for 60 seconds. After 20kg of titanium powder was added in its entirety, high-speed shearing at 8000rpm was continued for 20min. Followed by sonication at 3000Hz for 10min. And then pouring the mixture into a metal mold with the preheating temperature of 450 ℃, applying 100MPa pressure, maintaining the pressure for 10min, and obtaining the high-efficiency grain refiner for the Mg-40Ti novel rare earth magnesium alloy after solidification is completed. The whole melt treatment process is operated under the protection of nitrogen inert atmosphere. The size of the active nucleation titanium particles in the prepared novel Mg-Ti novel high-efficiency grain refiner is 92 percent smaller than 5 mu m.
Example 7
25Kg of preheated pure magnesium is placed at the bottom of a crucible for heating and smelting, after the temperature of the melt is raised to the temperature that the pure magnesium is completely melted, 25kg of zirconium powder with the average grain size of 10 mu m, which is preheated at 350 ℃ for 45min, is added into the pure magnesium melt, and after 1kg of zirconium powder is added, high-speed shearing at 6000rpm is applied for 60s. After 25kg of zirconium powder was added in its entirety, high-speed shearing at 6000rpm was continued for 20min. Followed by sonication at 3000Hz for 10min. And then pouring the mixture into a die with the preheating temperature of 400 ℃, applying 120MPa pressure, maintaining the pressure for 8 minutes, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-50Zr after solidification is completed. The whole melt processing process is operated under atmosphere protection. The active nucleation Zr particle size in the prepared novel Mg-Zr high-efficiency grain refiner is less than 5 mu m in 95 percent.
The novel grain refiner is used for refining melt grains of 800kg of Mg-Gd-Y alloy, and the Mg-8.5Gd-3.5Y-1.5Zn-0.55Zr semicontinuous cast ingot with the diameter of 450mm is prepared by semicontinuous casting, and the grains of the core and the edge tissues are fine and uniform, and the average grain size is about 35 mu m to 50 mu m. After multidirectional cogging forging, 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 breaking is more than 6%. The weight of the novel grain refiner is 25% of that of Mg-30Zr refiner prepared by the traditional molten salt method.
Example 8
And placing 20kg of preheated pure magnesium and pure zinc into the bottom of a crucible, heating and smelting, controlling the temperature at 550 ℃, and preserving the heat for 60 minutes to prepare the semi-solid slurry with the name 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. At the same time, a high-speed shearing treatment was applied to the middle of the semi-solid slurry, and after each addition of 2kg of zirconium powder, a high-speed shearing at 8000rpm was applied for 60 seconds. After 20kg of zirconium powder was added in its entirety, high-speed shearing at 8000rpm was continued for 10min. The melt temperature was then raised to 680℃and high shear at 8000rpm was continued for 10min and 4000Hz sonication was continued for 10min. And then pouring the melt into a die with the preheating temperature of 450 ℃, applying 100MPa pressure, maintaining the pressure for 10min, and obtaining the novel efficient grain refiner for the rare earth magnesium alloy of Mg-15Cu-50Zr after solidification is completed. The particle size of the active nucleation zirconium titanium infinite solid solution in the novel Mg-Cu-Zr high-efficiency grain refiner is less than 5 mu m at 95%.
The novel grain refiner is used for refining melt grains of 1000kg of Mg-Gd-Y alloy, and the Mg-9Gd-3Y-1.5Cu-0.55Zr semicontinuous cast ingot with the diameter of 450mm is prepared by semicontinuous casting, and the grains of the structures at the core part and the edge part are fine and uniform, and the average grain size is about 40-60 mu m. After extrusion with the extrusion ratio of 9, after T5 heat treatment, the mechanical properties of the bar at room temperature are measured: tensile strength is more than 520MPa, and elongation after breaking is more than 6%. 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) placing 15kg of preheated pure magnesium and pure zinc into the bottom of a crucible, heating and smelting, controlling the temperature at 600 ℃, and preserving the heat for 60 minutes to prepare the semi-solid slurry with the name and meaning of Mg-20 Ni. 15kg of zirconium powder having an average grain size of 100 μm preheated at 450℃for 60min was added to the Mg-Ni alloy semi-solid slurry. At the same time, a high-speed shearing treatment was applied to the middle of the semi-solid slurry, and after each 1.5kg of zirconium powder was added, a high-speed shearing at 6000rpm was applied for 30 seconds. After 15kg of zirconium powder was added in its entirety, high-speed shearing at 6000rpm was continued for 15min. The melt temperature was then raised to 680℃and high shear at 6000rpm was continued for 5min and 3000Hz sonication was continued for 10min. And then pouring the melt into a die 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 is completed. The 90% of active nucleation zirconium titanium infinite solid solution particle size in the prepared novel Mg-Ni-Zr high-efficiency grain refiner is smaller than 5 mu m.
The novel grain refiner is used for refining melt grains of 800kg of Mg-Gd-Y alloy, and the semi-continuous casting ingot of Mg-8.5Gd-3.5Y-1.2Ni-0.5Zr with the diameter of 420mm is prepared by semi-continuous casting, and the grains of the core and the edge tissues are fine and uniform, and the average grain size is about 30 mu m to 60 mu m. After extrusion with the extrusion ratio of 9, after T5 heat treatment, the mechanical properties of the bar at room temperature are measured: the tensile strength is above 510MPa, and the elongation after breaking is above 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
And (3) placing 15kg of preheated pure magnesium, pure zinc and pure copper at the bottom of a crucible, heating and smelting, controlling the temperature at 470 ℃, and preserving the temperature for 60 minutes to prepare the semi-solid slurry with the name and meaning of Mg-20Zn-10 Cu. 10kg of zirconium powder and titanium powder having an average grain size of 50 μm, preheated at 450℃for 60 minutes, were added to the Mg-Zn-Cu alloy semi-solid slurry. At the same time, a high-speed shearing treatment was applied to the middle of the semi-solid slurry, and after each 1kg of titanium/zirconium powder was added, a high-speed shearing at 8000rpm was applied for 60 seconds. After 10kg of zirconium powder and titanium powder were all added, high-speed shearing at 8000rpm was continued for 10min. The melt temperature was then raised to 680℃and high shear at 8000rpm was continued for 10min and 4000Hz sonication was continued for 10min. And then pouring the melt into a die with the preheating temperature of 500 ℃, applying 100MPa pressure, 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 is completed. The particle size of the active nucleation zirconium titanium infinite solid solution in the novel Mg-Zn-Cu-Ti/Zr high-efficiency grain refiner is less than 5 mu m at 95%.
The novel grain refiner is used for refining melt grains of 1000kg of Mg-Gd alloy, and the Mg-13.5Gd-1Zn-0.5Cu-0.5Ti/Zr semicontinuous cast ingot with the diameter of 450mm is prepared by semicontinuous casting, the grains of the core and the edge tissues are fine and uniform, and the average grain size is about 20 mu m to 50 mu m. After extrusion with the extrusion ratio of 9, after T5 heat treatment, the mechanical properties of the bar at room temperature are measured: the tensile strength is more than 550MPa, and the elongation after breaking 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
The Mg-30Zr prepared by the traditional molten salt method is used as 36kg of refiner for refining melt grains of 300kg of Mg-Gd-Y alloy, and after T6 treatment, the tensile property of a room temperature casting body is measured for a large complex casting of Mg-6.5Gd-3.5Y-0.6Zr prepared by low-pressure casting: the tensile strength is 310-330 MPa, and the elongation after breaking is 3-4.5%. As-cast Mg-6.5Gd-3.5Y-0.6Zr alloy microstructure treated with conventional Mg-30Zr refiner as shown in FIG. 4.
Comparative example 2
The Mg-30Zr prepared by the traditional molten salt method is used as 88kg of refiner for refining melt grains of 800kg of Mg-Gd-Y alloy, and large-specification cast ingots with the diameter of 450mm are prepared by semi-continuous casting, and the core structure and the edge structure of the prepared Mg-8.5Gd-3.5Y-1.5Zn-0.55Zr have fine internal and external grains, uniform grain sizes and average grain sizes of about 80-100 mu m. After multidirectional cogging forging, T5 heat treatment, the sampling tensile strength of the forging stock with the diameter of more than 1000mm in all directions is 350-370 MPa, and the elongation after breaking is 3-5%. The Mg-30Zr refining agent is added according to the content of more than 5 percent of the alloy Zr.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (6)
1. The preparation method of the grain refiner for the rare earth magnesium alloy is characterized by comprising the following steps of:
Adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into pure magnesium melt or semi-solid molten magnesium alloy, applying high-speed shearing and ultrasonic treatment, and solidifying to obtain the 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 comprises the following steps:
Heating pure magnesium to a complete melting state to obtain pure magnesium melt; then adding the well weighed and fully preheated titanium powder, zirconium powder or uniformly mixed titanium/zirconium powder into a pure magnesium melt, and applying high-speed shearing treatment and ultrasonic treatment in the process of adding the powder to obtain a magnesium melt containing titanium element or zirconium element or uniformly distributed titanium/zirconium element; then pouring the melt into a mould, solidifying under the action of pressure, and preparing the grain refiner for the rare earth magnesium alloy after the melt is completely solidified, wherein the whole preparation process is carried out under the protection of a vacuum environment or an inert atmosphere; 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 adding 1 part, and continuously applying high-speed shearing for 10-60 min after the powder is completely added, and then applying ultrasonic treatment, wherein the ultrasonic treatment process parameter is 2000-5000 Hz, and the ultrasonic treatment time is 2-15 min; the solidification process is to pour a magnesium melt containing titanium or zirconium or titanium/zirconium element into a metal mold with the preheating temperature of 300-600 ℃, and apply pressure of 60-150 MPa, and keep the pressure for 5-30 min;
The preparation method comprises the steps of adding preheated titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder into the semi-solid molten magnesium alloy, and preparing the grain refiner for the rare earth magnesium alloy, wherein 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 the semi-solid molten magnesium alloy, applying high-speed shearing treatment in the process of adding the powder, heating the magnesium alloy to a complete melting state after the powder is fully added, applying high-speed shearing and ultrasonic treatment to obtain magnesium alloy melt containing titanium element or zirconium element or titanium/zirconium element, pouring the magnesium alloy melt into a preheated mold, solidifying under the action of pressure, and preparing the grain refiner for the rare earth magnesium alloy after complete solidification, wherein the whole preparation process is carried out under the protection of vacuum environment or inert atmosphere;
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, wherein the rotating speed of a rotor is 6000-20000 rpm; after the powder is fully 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, 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 applied, wherein the ultrasonic treatment technological parameters are 3000 Hz-5000 Hz, and the ultrasonic treatment time is 5 min-30 min; the solidification process is to pour a magnesium melt containing titanium or zirconium or titanium/zirconium element into a metal mold with the preheating temperature of 300-600 ℃, apply pressure of 80-150 MPa and keep the pressure for 5-30 min.
2. The method for preparing a 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 pure magnesium melt to prepare the grain refiner for rare earth magnesium alloy, the grain refiner for rare earth magnesium alloy comprises the following components in percentage by mass: 30% -70% of Ti or Zr or Ti/Zr, and the balance of Mg.
3. The method for preparing a 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 a semi-solid molten magnesium alloy, and when the grain refiner for rare earth magnesium alloy is prepared, the semi-solid molten magnesium alloy is Mg-TM system, wherein TM is one or more of Zn, cu and Ni elements; the grain refiner for the rare earth magnesium alloy comprises the following components in percentage by mass: 10 to 30 percent of TM,30 to 60 percent of Ti or Zr or Ti/Zr, and the balance of Mg.
4. The method for preparing a grain refiner for rare earth magnesium alloy according to claim 1, wherein the average grain size of the titanium powder or zirconium powder or uniformly mixed titanium/zirconium powder is 0.001 μm to 1000 μm.
5. Grain refiner for rare earth magnesium alloy, characterized in that the grain refiner for rare earth magnesium alloy is prepared according to the preparation method of the grain refiner for rare earth magnesium alloy according to one of claims 1 to 4, wherein 85% -99.9% of active nucleation Ti or Zr or Ti/Zr particles in the grain refiner for rare earth magnesium alloy are smaller than 5 μm in size.
6. The application method of the grain refiner for the rare earth magnesium alloy is characterized by comprising the following steps of:
Weighing raw materials with corresponding weight according to the components of the magnesium alloy and the mass percentages thereof, adding the grain refiner according to claim 5 after the raw materials are completely melted and skimmed, and stirring after the raw materials are completely melted, and then refining; after refining, removing slag, standing, and using the prepared melt for preparing rare earth magnesium alloy castings.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820661A (en) * | 2014-02-27 | 2014-05-28 | 上海交通大学 | Preparation method of semisolid slurry of rare earth magnesium alloy |
| CN105385863A (en) * | 2015-11-23 | 2016-03-09 | 上海航天精密机械研究所 | Method for manufacturing magnesium-zirconium intermediate alloy through ultrasonic treatment |
| CN106435314A (en) * | 2016-12-01 | 2017-02-22 | 安徽工业大学 | Zirconium/magnesium oxide grain refiner and preparation method and application thereof |
| CN113444909A (en) * | 2021-06-08 | 2021-09-28 | 上海航天精密机械研究所 | Grain refinement method for large-size semi-continuous casting magnesium alloy ingot |
| CN113444910A (en) * | 2021-06-08 | 2021-09-28 | 上海航天精密机械研究所 | Magnesium alloy grain refiner and preparation method thereof |
| CN114058891A (en) * | 2021-11-25 | 2022-02-18 | 河北钢研德凯科技有限公司 | Method for adding zirconium element in smelting of zirconium-containing rare earth casting magnesium alloy |
| CN114262811A (en) * | 2021-12-23 | 2022-04-01 | 上海交通大学 | Method for improving magnesium alloy refining effect of Mg-Zr intermediate alloy |
| CN114703388A (en) * | 2022-04-12 | 2022-07-05 | 重庆大学 | Method for refining Mn-containing Mg-Zn-Al series cast magnesium alloy grains |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225464B (en) * | 2011-06-10 | 2013-07-10 | 深圳市新星轻合金材料股份有限公司 | Aluminum-zirconium-titanium-carbon (Al-Zr-Ti-C) grain refiner for magnesium and magnesium alloy and preparation method thereof |
| CN109055790B (en) * | 2018-08-16 | 2020-07-24 | 北京科技大学广州新材料研究院 | Grain refinement method of magnesium and magnesium alloy |
-
2022
- 2022-10-31 CN CN202211351355.6A patent/CN115652155B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820661A (en) * | 2014-02-27 | 2014-05-28 | 上海交通大学 | Preparation method of semisolid slurry of rare earth magnesium alloy |
| CN105385863A (en) * | 2015-11-23 | 2016-03-09 | 上海航天精密机械研究所 | Method for manufacturing magnesium-zirconium intermediate alloy through ultrasonic treatment |
| CN106435314A (en) * | 2016-12-01 | 2017-02-22 | 安徽工业大学 | Zirconium/magnesium oxide grain refiner and preparation method and application thereof |
| CN113444909A (en) * | 2021-06-08 | 2021-09-28 | 上海航天精密机械研究所 | Grain refinement method for large-size semi-continuous casting magnesium alloy ingot |
| CN113444910A (en) * | 2021-06-08 | 2021-09-28 | 上海航天精密机械研究所 | Magnesium alloy grain refiner and preparation method thereof |
| CN114058891A (en) * | 2021-11-25 | 2022-02-18 | 河北钢研德凯科技有限公司 | Method for adding zirconium element in smelting of zirconium-containing rare earth casting magnesium alloy |
| CN114262811A (en) * | 2021-12-23 | 2022-04-01 | 上海交通大学 | Method for improving magnesium alloy refining effect of Mg-Zr intermediate alloy |
| CN114703388A (en) * | 2022-04-12 | 2022-07-05 | 重庆大学 | Method for refining Mn-containing Mg-Zn-Al series cast magnesium alloy grains |
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