CN101693969B - Mg-Al-based alloy Al-Mn grain refiner, preparation method and using method thereof - Google Patents
Mg-Al-based alloy Al-Mn grain refiner, preparation method and using method thereof Download PDFInfo
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- CN101693969B CN101693969B CN2009101878652A CN200910187865A CN101693969B CN 101693969 B CN101693969 B CN 101693969B CN 2009101878652 A CN2009101878652 A CN 2009101878652A CN 200910187865 A CN200910187865 A CN 200910187865A CN 101693969 B CN101693969 B CN 101693969B
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Abstract
The invention relates to an Mg-Al-based alloy Al-Mn grain refiner, a preparation method and a using method thereof. The refiner comprises the components by weight percent: 25-35% of Al and 65-75% of Mn. The preparation method comprises the following steps: (1) blending according to the weight percent of the components of the grain refiner, adding excess metal Mn and obtaining mixed metal; (2) washing the mixed metal; (3) putting the washed mixed metal into an electric arc furnace, vacuumizing and filling argon gas into the electric arc furnace for smelting for four times; and (4) putting the mixed metal inside a closed container, vacuumizing and filling argon gas into the container, heating and carrying out heat preservation for 24-72h, and finally taking out and water quenching. The using method comprises the steps of adding the Al-Mn grain refiner in the liquid, evenly stirring and standing for 20-60min when Mg-Al-based alloy melt liquid is at the temperature of 700-750 DEG C. The preparation method and the using method of the Mg-Al-based alloy Al-Co grain refiner are simple, and the volume of addition and the refining effect of the Al-Co grain refiner are easily controlled, so that the aim of very good refining can be achieved by adding trace the Al-Co grain refiner, and the refining effect does not fade within 1h.
Description
Technical field
The present invention relates to a kind of grain-refining agent and preparation method thereof and using method, be specifically related to the Al-Mn grain refiner and preparation method thereof and the using method of a kind of Mg-Al of being used for base alloy.
Background technology
Though magnesium alloy has wide application prospect in all fields of traffic, aerospace and communication, enlarge the Application of Magnesium scope, also must solve the problem that magnesium and alloy self thereof exist.Magnesium and alloy substrate thereof are close-packed hexagonal structure, have only a basal slip system under the room temperature, and the deformation at room temperature ability is difficult to shape; The chemical property of magnesium is active, and standard potential is very low, and the natural oxide film of formation is fine and close inadequately, so corrosion stability of magnesium alloy is very poor; The room temperature strength of magnesium alloy is low, the not enough 300MPa of the tensile strength of cast magnesium alloys, and wrought magnesium alloys undercapacity 400MPa can not satisfy the performance requriements of load spare.And grain refining is to address the above problem, and improves the important means of as-cast magnesium alloy and over-all properties thereof.
At present, the method for Mg-Al based alloy grain refinement has a variety of, and as overheated method, carbonaceous breeds method, microalloying etc.Generally to breed method be to add C in magnesium alloy to the carbonaceous of Cai Yonging
2Cl
6Or CCl
4, these alterants produce chlorine after adding, environment and human body are produced serious harm, and (20～30min) its thinning effects are taking off easily just, need carry out secondary metamorphic and handle in very short time.Some investigators also by adding Mg-Al-C, Al-C, Al-Ti-C master alloy, add pure Al
4C
3, mode refining Mg-Al-based alloy such as SiC particle, but these alloys and particle preparation technology are comparatively complicated.
Summary of the invention
At the problem of the Al-Mn grain refiner complicated process of preparation of existing Mg-Al base alloy, the invention provides a kind of Al-Mn grain refiner and preparation method thereof and using method of Mg-Al base alloy
The composition of Al-Mn grain refiner of the present invention is Al 25～35% by weight percentage, Mn65～75%.
The preparation method of Al-Mn grain refiner of the present invention carries out according to the following steps:
1, the moiety weight percent by grain-refining agent is Al 25～35%, and Mn65～75% batching adds excessive manganese metal simultaneously, and excessive manganese metal accounts for batching with 5～15% of manganese metal gross weight, obtains hybrid metal.Wherein adding excessive manganese metal is the scaling loss part.
2, hybrid metal is cleaned, purging method is to be under the ultrasonic wave condition of 40～60KHz in frequency with hybrid metal, cleans with organic solvent ethanol or acetone, and scavenging period is 3～5min.
3, the hybrid metal after will cleaning places electric arc furnace, then electric arc furnace is vacuumized, and charging into argon gas to electric arc furnace internal gas pressure again is 0.02～0.04MPa; Hybrid metal is carried out four meltings, and the voltage that applies during melting is 20～45V, and electric current is 200～350A, each melting time spent 2～3min; When being vacuumized, electric arc furnace require air pressure 1 * 10
-3～5 * 10
-3MPa.
4, the hybrid metal after four meltings places encloses container, encloses container is vacuumized, charging into argon gas to the air pressure in the encloses container again is to seal behind 0.35～0.4MPa, encloses container is heated to 950～1150 ℃ again, insulation 24～72h, hybrid metal is taken out shrend, obtain Al-Mn grain refiner.Wherein encloses container vacuumizes and requires air pressure 1 * 10
-2～5 * 10
-2MPa.
The using method of Al-Mn grain refiner of the present invention is:
During melting Mg-Al base alloy, at Mg-Al base alloy melt temperature is under 700～750 ℃ of conditions, the Al-Mn grain refiner of aluminium foil parcel is placed Mg-Al base alloy liquation, leave standstill 20～60min after stirring, the add-on of Al-Mn grain refiner is 0.5～2.5% of a Mg-Al base alloy liquation gross weight.
Leave standstill and finish back slagging-off, cast, the average refinement rate of crystal grain of the Mg-Al base alloy of acquisition is 40～43%.
The Al-Mn grain refiner that preparation method of the present invention obtains is blocky aluminium manganese master alloy product, and this aluminium manganese master alloy contains AlMn intermetallic compound phase, plays heterogeneous forming core effect in joining magnesium alloy fused mass, thus the crystal grain of refinement magnesium alloy.Product preparation method of the present invention and using method are simple, and the addition of product and thinning effect are easy to control, add the purpose can reach fine refinement with trace, and thinning effect taking off not in 1h.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the Al-Mn grain refiner of preparation in the embodiment of the invention 1, and a is an aluminium manganese phase among the figure.
Fig. 2 is the metallography microscope photo figure of the 0#AZ31 magnalium base alloy in the embodiment of the invention 1.
Fig. 3 is the metallography microscope photo figure of the 1#AZ31 magnalium base alloy in the embodiment of the invention 1.
Fig. 4 is the metallography microscope photo figure of the 2#AZ31 magnalium base alloy in the embodiment of the invention 1.
Fig. 5 is the metallography microscope photo figure of the 3#AZ31 magnalium base alloy in the embodiment of the invention 1.
Fig. 6 is the metallography microscope photo figure of the 4#AZ31 magnalium base alloy in the embodiment of the invention 1.
Fig. 7 is the metallography microscope photo figure of the 5#AZ31 magnalium base alloy in the embodiment of the invention 1.
Embodiment
Weight purity 〉=99.99% of the metallic aluminium that adopts in the embodiment of the invention, weight purity 〉=99.88% of manganese metal, weight purity 〉=99.99% of metallic zinc, weight purity 〉=99.95% of MAGNESIUM METAL.
The ethanol that adopts in the embodiment of the invention is industrial spirit, and the acetone of employing is industrial acetone.
The ultrasonic equipment model that adopts in the embodiment of the invention is KUDOS-SK3300LHC.
The encloses container that adopts in the embodiment of the invention is a silica tube.
The resistance furnace that adopts in the embodiment of the invention is a MRL-8 type well formula resistance furnace.
The crucible that adopts in the embodiment of the invention is the high-strength graphite crucible.
The angle grinding machine that adopts in the embodiment of the invention is the solid VG100DE type angle of a German prestige grinding machine, and rotating speed is 500r/min during work.
Embodiment 1
With metallic aluminium and manganese metal mix, wherein metallic aluminium accounts for 25% of mixture by weight percentage, and manganese metal accounts for 75% of mixture by weight percentage, adds excessive manganese metal simultaneously, excessive manganese metal accounts for batching with 15% of manganese metal gross weight, obtains hybrid metal.
Hybrid metal is cleaned with organic solvent under the ultrasonic wave condition, and scavenging period is 3min, and wherein ultrasonic frequency is 40KHz, and organic solvent is an ethanol.
Hybrid metal after cleaning is placed electric arc furnace, and it is 1 * 10 that electric arc furnace is evacuated to air pressure
-3MPa, charging into argon gas to electric arc furnace internal gas pressure again is 0.02MPa.
Hybrid metal is carried out melting, and the voltage that applies during melting is 45V, and electric current is 200A, melting time spent 2min.Carry out four meltings as stated above repeatedly.
Hybrid metal after four meltings is placed encloses container, and then encloses container being evacuated to air pressure is 1 * 10
-2MPa, charging into argon gas to the air pressure in the encloses container again is to seal behind the 0.35MPa, encloses container is heated to 1000 ℃ again, insulation 72h takes out shrend with hybrid metal, obtains Al-Mn grain refiner, its composition is Al 25% by weight percentage, Mn75%, and the X-ray diffraction spectrogram is shown in Figure 1.
Adopt metallic aluminium, MAGNESIUM METAL, metallic zinc to prepare AZ31 magnalium base alloy; with metallic aluminium, MAGNESIUM METAL, metallic zinc as requested proportioning get the raw materials ready; then respectively with angle grinding machine polishing light; put into loft drier again, under 200 ℃ of conditions, heat 10min, put into the crucible that cleans up then; crucible is placed resistance furnace; be heated to 400～500 ℃, feed shielding gas, shielding gas is N
2+ SF
6Mixed gas, nitrogen and SF in the mixed gas
6The blending ratio of gas is 1000: 2 by volume.
Continuing heating resistor stove to temperature is 750 ℃, metal all melts in the crucible, to join in the molten metal with the Al-Mn grain refiner of aluminium foil parcel, it all is 0.5% of Mg-Al base alloy liquation gross weight that add-on is respectively, 1%, 1.5%, 2%, 2.5%, leave standstill 40min after stirring.
Leaving standstill the oxide slag body of taking the alloy molten surface after the end off, being poured into preheating temperature is in 250 ℃ the irony mold, add-on by Al-Mn grain refiner is 0.5% of a Mg-Al base alloy liquation gross weight, 1%, 1.5%, 2%, 2.5%, obtain 1#, 2#, 3#, 4#, 5#AZ31 magnalium base alloy respectively, its metallography microscope photo is respectively shown in Fig. 3,4,5,6,7.
Preparation AZ31 magnalium base alloy under the situation that does not add Al-Mn grain refiner obtains 0#AZ31 magnalium base alloy as stated above, and its metallography microscope photo as shown in Figure 2.
By Fig. 2,3,4,5,6,7 as seen, behind the use Al-Mn grain refiner, compare with not using grain-refining agent, the average grain size of AZ31 magnalium base alloy is reduced to 50～55 μ m by 92 μ m, and refinement efficient reaches 40～43%.
Embodiment 2
With metallic aluminium and manganese metal mix, wherein metallic aluminium accounts for 35% of mixture by weight percentage, and manganese metal accounts for 65% of mixture by weight percentage, adds excessive manganese metal then, excessive manganese metal accounts for batching with 5% of manganese metal gross weight, obtains hybrid metal.
Hybrid metal is cleaned with organic solvent under the ultrasonic wave condition, and scavenging period is 5min, and wherein ultrasonic frequency is 60KHz, and organic solvent is an ethanol.
Hybrid metal after cleaning is placed electric arc furnace, and it is 5 * 10 that electric arc furnace is evacuated to air pressure
-3MPa, charging into argon gas to electric arc furnace internal gas pressure again is 0.04MPa.
Hybrid metal is carried out melting, and the voltage that applies during melting is 30V, and electric current is 270A, melting time spent 3min.Carry out four meltings as stated above repeatedly.
Hybrid metal after four meltings is placed encloses container, then encloses container is evacuated to air pressure 3 * 10
-2MPa, charging into argon gas to the air pressure in the encloses container again is to seal behind the 0.4MPa, encloses container is heated to 1150 ℃ again, and insulation 24h takes out shrend with hybrid metal, obtains Al-Mn grain refiner, and its composition is Al 35% by weight percentage, Mn65%.
Adopt metallic aluminium, MAGNESIUM METAL, metallic zinc to prepare AZ31 magnalium base alloy; with metallic aluminium, MAGNESIUM METAL, metallic zinc as requested proportioning get the raw materials ready; then respectively with angle grinding machine polishing light; put into loft drier again, under 200 ℃ of conditions, heat 10min, put into the crucible that cleans up then; crucible is placed resistance furnace; be heated to 400～500 ℃, feed shielding gas, shielding gas is N
2+ SF
6Mixed gas, nitrogen and SF in the mixed gas
6The blending ratio of gas is 1000: 2 by volume.
Continuing heating resistor stove to temperature is 700 ℃, metal all melts in the crucible, to join in the molten metal with the Al-Mn grain refiner of aluminium foil parcel, it all is 0.5% of Mg-Al base alloy liquation gross weight that add-on is respectively, 1%, 1.5%, 2%, 2.5%, leave standstill 60min after stirring.
Leave standstill and finish the back by embodiment 1 described method slagging-off, cast, compare with not using grain-refining agent, the average refinement rate of crystal grain of the Mg-Al base alloy of acquisition is 40～43%.
Embodiment 3
With metallic aluminium and manganese metal mix, wherein metallic aluminium accounts for 30% of mixture by weight percentage, and manganese metal accounts for 70% of mixture by weight percentage, adds excessive manganese metal then, excessive manganese metal accounts for batching with 10% of manganese metal gross weight, obtains hybrid metal.
Hybrid metal is cleaned with organic solvent under the ultrasonic wave condition, and scavenging period is 4min, and wherein ultrasonic frequency is 50KHz, and organic solvent is an acetone.
Hybrid metal after cleaning is placed electric arc furnace, and it is 3 * 10 that electric arc furnace is evacuated to air pressure
-3MPa, charging into argon gas to electric arc furnace internal gas pressure again is 0.03MPa.
Hybrid metal is carried out melting, and the voltage that applies during melting is 150V, and electric current is 10A, and melting time spent 2.5min carries out four meltings as stated above repeatedly.
Hybrid metal after four meltings is placed encloses container, then encloses container is evacuated to air pressure 5 * 10
-2MPa, charging into argon gas to the air pressure in the encloses container again is to seal behind the 0.38MPa, encloses container is heated to 950 ℃ again, and insulation 48h takes out shrend with hybrid metal, obtains Al-Mn grain refiner, and its composition is Al 30% by weight percentage, Mn70%.
Adopt metallic aluminium, MAGNESIUM METAL, metallic zinc to prepare AZ31 magnalium base alloy; with metallic aluminium, MAGNESIUM METAL, metallic zinc as requested proportioning get the raw materials ready; then respectively with angle grinding machine polishing light; put into loft drier again, under 200 ℃ of conditions, heat 10min, put into the crucible that cleans up then; crucible is placed resistance furnace; be heated to 400～500 ℃, feed shielding gas, shielding gas is N
2+ SF
6Mixed gas, nitrogen and SF in the mixed gas
6The blending ratio of gas is 1000: 2 by volume.
Continuing heating resistor stove to temperature is 720 ℃, metal all melts in the crucible, to join in the molten metal with the Al-Mn grain refiner of aluminium foil parcel, it all is 0.5% of Mg-Al base alloy liquation gross weight that add-on is respectively, 1%, 1.5%, 2%, 2.5%, leave standstill 20min after stirring.
Leave standstill and finish the back by embodiment 1 described method slagging-off, cast, compare with not using grain-refining agent, the average refinement rate of crystal grain of the Mg-Al base alloy of acquisition is 40～43%.
Claims (3)
1. the preparation method of the Al-Mn grain refiner of Mg-Al base alloy, it is characterized in that carrying out according to the following steps: (1) is Al 25～35% by the moiety weight percent of grain-refining agent, Mn65～75% batching, add excessive manganese metal simultaneously, excessive manganese metal accounts for batching with 5～15% of manganese metal gross weight, obtains hybrid metal; (2) hybrid metal is cleaned; (3) hybrid metal after will cleaning places electric arc furnace, then electric arc furnace is vacuumized, and charging into argon gas to electric arc furnace internal gas pressure again is 0.02～0.04MPa; Hybrid metal is carried out four meltings, and the voltage that applies during melting is 20～45V, and electric current is 200～350A, each melting time spent 2～3min; (4) hybrid metal after four meltings places encloses container, encloses container is vacuumized, charging into argon gas to the air pressure in the encloses container again is to seal behind 0.35～0.4MPa, encloses container is heated to 950～1150 ℃ again, insulation 24～72h, take out the hybrid metal shrend, obtain Al-Mn grain refiner.
2. the preparation method of the Al-Mn grain refiner of Mg-Al base alloy according to claim 1, it is characterized in that described hybrid metal is cleaned is to be under the ultrasonic wave condition of 40～60KHz in frequency with hybrid metal, clean with organic solvent ethanol or acetone, scavenging period is 3～5min.
3. the preparation method of the Al-Mn grain refiner of Mg-Al base alloy according to claim 1 is characterized in that electric arc furnace is vacuumized in the described step (3): require air pressure 1 * 10
-3～5 * 10
-3MPa.
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| CN106062224B (en) * | 2014-04-10 | 2018-02-06 | 韩国机械研究院 | The manufacture method of grain refiner for magnesium alloy, magnesium alloy comprising aluminium and the magnesium alloy using this method manufacture |
| CN104195359B (en) * | 2014-07-16 | 2017-03-01 | 沈阳航空航天大学 | A kind of high Mn content aluminum manganese intermediate alloy and preparation method thereof |
| CN107419127A (en) * | 2017-06-30 | 2017-12-01 | 常州市瑞泰物资有限公司 | A kind of magnesium alloy refiner and preparation method thereof |
| CN113215430B (en) * | 2021-04-30 | 2022-03-01 | 上海交通大学 | Method for improving Zr yield in process of refining magnesium alloy by Zr salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472350A (en) * | 2003-06-19 | 2004-02-04 | 上海交通大学 | Composite melting agent for reinfing crystal grains of aluminium magnesium alloy and preparation thereof |
| CN101481766A (en) * | 2008-12-08 | 2009-07-15 | 清华大学 | Mn-Al intermediate alloy, and preparation and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472350A (en) * | 2003-06-19 | 2004-02-04 | 上海交通大学 | Composite melting agent for reinfing crystal grains of aluminium magnesium alloy and preparation thereof |
| CN101481766A (en) * | 2008-12-08 | 2009-07-15 | 清华大学 | Mn-Al intermediate alloy, and preparation and use thereof |
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