CN101440450A - Preparation of lanthanum-containing AE heat resisting die-casting magnesium alloy - Google Patents

Preparation of lanthanum-containing AE heat resisting die-casting magnesium alloy Download PDF

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Publication number
CN101440450A
CN101440450A CNA2008100509798A CN200810050979A CN101440450A CN 101440450 A CN101440450 A CN 101440450A CN A2008100509798 A CNA2008100509798 A CN A2008100509798A CN 200810050979 A CN200810050979 A CN 200810050979A CN 101440450 A CN101440450 A CN 101440450A
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China
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magnesium
alloy
lanthanum
minutes
percent
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CNA2008100509798A
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Chinese (zh)
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孟健
张景怀
唐定骧
张德平
房大庆
王鸿燕
杜海
鲁化一
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to a lanthanum contained AE series heat-resistant die-casting magnesium alloy and a preparation method thereof. The alloy consists of the following compositions by mass percentage: 3.5 to 4.5 percent of Al, 1 to 6 percent of La, 0.2 to 0.6 percent of Mn, and less than 0.03 percent of gross of impurity elements Fe, Cu and Ni, and the balance being magnesium. The method comprises the following steps: preheating pure magnesium, aluminum, aluminum-manganese interalloy and magnesium-lanthanum interalloy to the temperature of 200 DEG C according to a proportion; then, putting the mixture into a crucible which is preheated to the temperature of 300 DEG C, and introducing shield gas with a volume ratio of SF6 to CO2 being 1:100; adding the magnesium-lanthanum interalloy into the crucible after melt reaching a temperature of between 720 and 740 DEG C; continuously introducing the shield gas to stir the melt for 5 to 10 minutes; introducing argon gas to refine the melt for 5 to 10 minutes; and keeping the mixture stand for 28 to 32 minutes to obtain the lanthanum contained AE series heat-resistant die-casting magnesium alloy. The alloy has tensile strength at 200 DEG C of between 119 and 136MPa, yield strength of between 85 and 107MPa, elongation percentage of between 18 and 24 percent, and creep rate under 70MPa at 200 DEG C of 1.17*10<-9>s<-1>.

Description

A kind of preparation method of lanthanum-containing AE heat resisting die-casting magnesium alloy
Technical field
The invention belongs to a kind of preparation method of lanthanum-containing AE heat resisting die-casting magnesium alloy.
Background technology
Magnesium alloy is the minimum structural metallic materials of density in engineering is used, simultaneously magnesium alloy have also that height ratio is strong, high damping, electromagnetic shielding and excellent casting, machinability and easy advantage such as recoverys, have important use value and wide application prospect in fields such as automobile, electronics, Aeronautics and Astronautics, national defence.Particularly in short supply day by day at metals resources such as global iron, aluminium, zinc, under environmental protection pressure and the awareness of saving energy enhanced overall background, resources advantage, the performance advantage of magnesium are not fully exerted, and magnesium alloy becomes a kind of engineering materials of rapid emergence.Two kinds of Mg-Al of AZ and AM are that diecast magnesium alloy is applied at auto industry field with its good die casting performance and higher room-temperature mechanical property, AZ91 for example, it is a kind of magnesium alloy of standard brand, it also is the maximum magnesium alloy of present industrial consumption, but being diecast magnesium alloy, AZ and AM have the shortcoming of resistance toheat difference, the long term operation temperature can not surpass 120 ℃, has therefore limited its range of application as lightweight structural material.Recent study shows, near the eutectic β-Mg under the high temperature crystal boundary 17Al 12Soften easily mutually and alligatoring, and under long hot conditions, oversaturated Al generates the discontinuous Mg that distributes along crystal boundary in the matrix 17Al 12Phase, the easily softening effect that does not have precipitation strength of precipitated phase, and the minimizing of solid solution Al atom reduces solution strengthening, thereby causes slippage of alloy crystal boundary and intracrystalline dislocation motion to become easily, and this is that Mg-Al is the major cause of alloy for die casting hot strength and creep-resistant property difference.
The investigator has done a large amount of research to heat resistance magnesium alloy both at home and abroad in recent years.Dow Magnesium is by to Mg-Al being the AE42 diecast magnesium alloy that adds cerium-rich rare earth (RE) research and development in the alloy, by generating heat-staple relatively Al 11RE 3Phase, and suppress Mg 17Al 12Generate mutually, improved the resistance toheat of alloy.But relevant report subsequently shows, when temperature is higher than 150 ℃, and Al 11RE 3Mg is decomposed and caused to part mutually 17Al 12The generation of phase makes to be organized near the alloy crystal boundary in the creep process unstablely, finally causes the alloy creep-resistant property sharply to descend.The novel anti high temperature creep diecast magnesium alloy AE44 of Norway Hydro magnesium industry company in 2005 exploitation, auto parts have been used to produce, the engine bracker of automobile for example, but because the rare earth that adds in the alloy is cerium-rich rare earth equally, thereby the alloy basic reason that creep property descends when being higher than 150 ℃, i.e. Al 11RE 3The part of phase is decomposed, and is not solved fully.Therefore be that diecast magnesium alloy can not satisfy alloy in 200 ℃ of requirements of using down of higher temperature by the AE that adds common cerium-rich mischmetal.
Summary of the invention
The purpose of this invention is to provide a kind of AE that contains lanthanum is heat-proof compression casting magnesium alloy;
The preparation method that it is heat-proof compression casting magnesium alloy that another object of the present invention provides a kind of AE that contains lanthanum.
At the weakness of present diecast magnesium alloy, it is heat-proof compression casting magnesium alloy that the AE that contains lanthanum is provided.It is cerium-rich mischmetal in the alloy that this alloy replaces traditional AE with pure lanthanum rare earth, a large amount of by generating, compare Al 11RE 3The Al that (RE represents cerium-rich mischmetal) is more stable 11La 3Phase has further improved the resistance toheat of alloy, and the life-time service temperature can reach 200 ℃; In addition, alloy adopts the high lanthanum element of ree distribution pattern as the alloying composition, ensures that this cost of alloy is low, sustainable supply.
The AE that contains lanthanum of the present invention's preparation is a heat-proof compression casting magnesium alloy, and its mass percent proportioning is: Al:3.5%~4.5%, and La:1%~6%, Mn:0.2%~0.6%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.
Preparation process is as follows:
At first, pure magnesium, aluminium, aluminium manganese master alloy and magnesium-lanthanum master alloy is preheating to 200 ℃, pure magnesium, aluminium, aluminium manganese master alloy is put into be preheating to 300 ℃ crucible then, and feed SF by the proportioning weighing 6: CO 2Volume ratio is the shielding gas of 1:100; after melting fully, the furnace charge that adds adds magnesium-lanthanum master alloy; and the logical shielding gas of continuation; stirred 5~10 minutes; logical then argon gas refining 5~10 minutes; left standstill after the refining 28-32 minute, when melt was cooled to 680 ℃, the AE that obtains containing lanthanum was a heat-proof compression casting magnesium alloy.Room temperature tensile strength: 225~251MPa, yield strength: 132~145MPa, unit elongation: 9~13%; Tensile strength in the time of 150 ℃: 150~170MPa, yield strength: 116~122MPa, unit elongation: 20~24%; Tensile strength in the time of 200 ℃: 119~136MPa, yield strength: 85~107MPa, unit elongation: 18~24%; At 200 ℃, the creep speed 1.17 * 10 under the 70MPa -9s -1
Characteristics of the present invention and beneficial effect:
1) aluminium is main alloy element in the alloy, and an amount of aluminium can make alloy obtain isostatic intensity, plasticity and casting technique performance, makes the present invention be fit to produce in batches.2) Rare Earth Lanthanum is the element that the present invention is used to improve alloy strength and resistance toheat, because lanthanum combines generation Al with aluminium in the alloy 11La 3Phase has suppressed the Mg of poor heat stability 17Al 12Generate mutually, help improving the high-temperature behavior of alloy; Secondly, the Al of generation 11La 3Have very high fusing point and thermostability mutually, fusing point is 1240 ℃, Al 11La 3And Al 11RE 3Compare and have higher thermostability, under 200 ℃ high temperature creep condition, the AE that contains lanthanum is near tissue, the i.e. Al crystal boundary of heat-proof compression casting magnesium alloy 11La 3The eutectic structure of phase and α-Mg keeps stable, does not have Al 11La 3The decomposition of phase is so lanthanum more can improve the resistance toheat of Mg-Al base diecast magnesium alloy than cerium-rich mischmetal; Once more, the outstanding microtexture of this type of alloy is to be formed near the tiny Al of crystal boundary 11La 3The orderly stacked structure of particulate, when alloy material bore higher stress, this structure can produce bigger distortion, reduced stress concentrations, and therefore making this type of AE that contains lanthanum is that heat-proof compression casting magnesium alloy has good intensity and plasticity simultaneously.In addition, the impurity when Rare Earth Lanthanum can be removed melting in the magnesium alloy fused mass reaches the degasification refining, purifies the effect of melt; Rare Earth Lanthanum is the surface active element of magnesium alloy, and rare earth forms MgO, La at alloy liquid surface aggregation during alloy melting 2O 3, Al 2O 3Etc. polynary composite compact oxide skin, alleviate oxidative phenomena, improve the combustion initiation temperature of alloy, help the founding of alloy; In the alloy liquid process of setting, Rare Earth Lanthanum improves the constitutional supercooling degree in the enrichment of solid-liquid forward position, helps the refinement alloy structure.Therefore Rare Earth Lanthanum helps to improve the over-all properties of alloy.3) effect of manganese mainly is the corrosion resistance nature that improves alloy, manganese can form compound with iron in the magnesium alloy or other heavy metal elements, its major part is excluded as slag, thereby eliminates/alleviate iron or other heavy metal elements harmful effect corrosion stability of magnesium alloy.
Embodiment
Embodiment 1
Take by weighing aluminium by mass percentage: 3.5%, lanthanum: 1.0%, manganese: 0.2%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.Pure magnesium, aluminium, aluminium manganese master alloy and magnesium-lanthanum master alloy is preheating to 200 ℃, pure magnesium, aluminium, aluminium manganese master alloy is put into be preheating to 300 ℃ crucible then, and feed SF 6: CO 2Volume ratio is the shielding gas of 1:100; after the furnace charge that adds melts fully, add magnesium-lanthanum master alloy when melt temperature reaches 720 ℃, and continue logical shielding gas; after adding magnesium-lanthanum master alloy fusing; stirred 5 minutes when temperature recovery to 720 ℃, logical then argon gas refining 5 minutes was left standstill after the refining 28 minutes; when melt is cooled to 680 ℃; carry out die casting on the cold-chamber die casting machine of 280KN clamp force, the AE that obtains containing lanthanum is a heat-proof compression casting magnesium alloy, and alloy property sees Table 1 and table 2.
Embodiment 2
Take by weighing aluminium by mass percentage: 4.0%, lanthanum: 2.0%, manganese: 0.3%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.Add magnesium-lanthanum master alloy when melt temperature reaches 725 ℃, stirred 8 minutes during temperature recovery to 725 ℃, logical then argon gas refining 7 minutes was left standstill after the refining 30 minutes, and all the other are with embodiment 1, and alloy property sees Table 1 and table 2.
Embodiment 3
Take by weighing aluminium by mass percentage: 4.2%, lanthanum: 4.2%, manganese: 0.4%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.Add magnesium-lanthanum master alloy when melt temperature reaches 730 ℃, stirred 10 minutes during temperature recovery to 730 ℃, logical then argon gas refining 10 minutes was left standstill after the refining 30 minutes, and all the other are with embodiment 1, and alloy property sees Table 1, table 2 and table 3.
Embodiment 4
Take by weighing aluminium by mass percentage: 4.5%, lanthanum: 6.0%, manganese: 0.6%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.Add magnesium-lanthanum master alloy when melt temperature reaches 740 ℃, stirred 10 minutes during temperature recovery to 730 ℃, logical then argon gas refining 10 minutes was left standstill after the refining 32 minutes, and all the other are with embodiment 1, and alloy property sees Table 1 and table 2.
The room-temperature mechanical property of table 1 embodiment of the invention 1, example 2, example 3 and example 4
The mechanical behavior under high temperature of table 2 embodiment of the invention 1, example 2, example 3 and example 4
The high-temperature creep resistance of table 3 embodiment of the invention 3 alloys

Claims (2)

1, a kind of AE that contains lanthanum is a heat-proof compression casting magnesium alloy, it is characterized in that, composition and mass percent thereof are: Al:3.5%~4.5%, and La:1%~6%, Mn:0.2%~0.6%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium.
2, a kind of AE that contains lanthanum as claimed in claim 1 preparation method that is heat-proof compression casting magnesium alloy, composition and mass percent thereof are: Al:3.5%~4.5%, La:1%~6%, Mn:0.2%~0.6%, the total amount of impurity element Fe, Cu and Ni is less than 0.03%, and surplus is a magnesium; At first, pure magnesium, aluminium, aluminium manganese master alloy and magnesium-lanthanum master alloy is preheating to 200 ℃, pure magnesium, aluminium, aluminium manganese master alloy is put into be preheating to 300 ℃ crucible then, and feed SF by the proportioning weighing 6: CO 2Volume ratio is the shielding gas of 1:100; after the furnace charge that adds melts fully; when reaching 720 ℃~740 ℃, melt temperature adds magnesium-lanthanum master alloy; and the logical shielding gas of continuation; stirred 5~10 minutes, logical then argon gas refining 5~10 minutes was left standstill after the refining 28-32 minute; when melt was cooled to 680 ℃, the AE that obtains containing lanthanum was a heat-proof compression casting magnesium alloy.
CNA2008100509798A 2008-07-18 2008-07-18 Preparation of lanthanum-containing AE heat resisting die-casting magnesium alloy Pending CN101440450A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102586662A (en) * 2011-01-14 2012-07-18 三井金属矿业株式会社 Magnesium alloy with high thermal conductivity for die-casting
US8293034B2 (en) 2010-01-22 2012-10-23 Modern Islands Co., Ltd. Lead-free brass alloy
CN102776427A (en) * 2012-08-17 2012-11-14 临江市东锋有色金属股份有限公司 Rare earth-containing heat-resisting magnesium alloy
CN103447433A (en) * 2013-09-04 2013-12-18 中南大学 Preparation method of large-sized magnesium alloy forged disc
CN103464765A (en) * 2013-09-12 2013-12-25 哈尔滨工程大学 Mg-Al-La/Al laminated composite and method for manufacturing same
CN104388715A (en) * 2014-12-15 2015-03-04 春兴精工(常熟)有限公司 Preparation method of high-yield-strength magnesium alloy
CN105463280A (en) * 2015-12-14 2016-04-06 山东华盛荣镁业科技有限公司 Magnesium alloy with high thermal conductivity and preparation method of magnesium alloy
CN106661682A (en) * 2015-05-07 2017-05-10 死海镁金属有限公司 Creep resistant, ductile magnesium alloys for die casting
CN107604228A (en) * 2017-08-30 2018-01-19 上海交通大学 Corrosion-resistant diecast magnesium alloy of high heat conduction and preparation method thereof
CN107900314A (en) * 2017-12-28 2018-04-13 重庆仟和镁业科技有限公司 The production technology of overall magnesium alloy chair framework
US10358703B2 (en) 2014-11-13 2019-07-23 Byd Company Limited Magnesium alloy and method of preparing the same
US10519530B2 (en) 2014-11-13 2019-12-31 Byd Company Limited Magnesium alloy and method of preparing the same
CN113322404A (en) * 2021-06-03 2021-08-31 哈尔滨工业大学 High-thermal-conductivity high-strength Mg-Al-La-Mn wrought magnesium alloy and preparation method thereof

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8293034B2 (en) 2010-01-22 2012-10-23 Modern Islands Co., Ltd. Lead-free brass alloy
CN102586662A (en) * 2011-01-14 2012-07-18 三井金属矿业株式会社 Magnesium alloy with high thermal conductivity for die-casting
CN102776427A (en) * 2012-08-17 2012-11-14 临江市东锋有色金属股份有限公司 Rare earth-containing heat-resisting magnesium alloy
CN103447433A (en) * 2013-09-04 2013-12-18 中南大学 Preparation method of large-sized magnesium alloy forged disc
CN103464765A (en) * 2013-09-12 2013-12-25 哈尔滨工程大学 Mg-Al-La/Al laminated composite and method for manufacturing same
CN103464765B (en) * 2013-09-12 2015-08-12 哈尔滨工程大学 A kind of Mg-Al-La/Al laminated composite materials and preparation method thereof
US10519530B2 (en) 2014-11-13 2019-12-31 Byd Company Limited Magnesium alloy and method of preparing the same
US10358703B2 (en) 2014-11-13 2019-07-23 Byd Company Limited Magnesium alloy and method of preparing the same
CN104388715A (en) * 2014-12-15 2015-03-04 春兴精工(常熟)有限公司 Preparation method of high-yield-strength magnesium alloy
CN106661682A (en) * 2015-05-07 2017-05-10 死海镁金属有限公司 Creep resistant, ductile magnesium alloys for die casting
US10751793B2 (en) 2015-05-07 2020-08-25 Dead Sea Magnesium Ltd. Creep resistant, ductile magnesium alloys for die casting
CN106661682B (en) * 2015-05-07 2019-10-11 死海镁金属有限公司 Creep resistant, extendable magnesium alloy for die casting
CN105463280A (en) * 2015-12-14 2016-04-06 山东华盛荣镁业科技有限公司 Magnesium alloy with high thermal conductivity and preparation method of magnesium alloy
CN105463280B (en) * 2015-12-14 2018-04-13 山东华盛荣镁业科技有限公司 A kind of magnesium alloy with high heat conductance and preparation method thereof
CN107604228B (en) * 2017-08-30 2019-09-27 上海交通大学 Corrosion-resistant diecast magnesium alloy of high thermal conductivity and preparation method thereof
CN107604228A (en) * 2017-08-30 2018-01-19 上海交通大学 Corrosion-resistant diecast magnesium alloy of high heat conduction and preparation method thereof
CN107900314B (en) * 2017-12-28 2019-09-03 重庆仟和镁业科技有限公司 The production technology of whole magnesium alloy chair framework
CN107900314A (en) * 2017-12-28 2018-04-13 重庆仟和镁业科技有限公司 The production technology of overall magnesium alloy chair framework
CN113322404A (en) * 2021-06-03 2021-08-31 哈尔滨工业大学 High-thermal-conductivity high-strength Mg-Al-La-Mn wrought magnesium alloy and preparation method thereof
CN113322404B (en) * 2021-06-03 2022-03-01 哈尔滨工业大学 High-thermal-conductivity high-strength Mg-Al-La-Mn wrought magnesium alloy and preparation method thereof

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