CN101985714B - High-plasticity magnesium alloy and preparation method thereof - Google Patents

High-plasticity magnesium alloy and preparation method thereof Download PDF

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CN101985714B
CN101985714B CN201010575745A CN201010575745A CN101985714B CN 101985714 B CN101985714 B CN 101985714B CN 201010575745 A CN201010575745 A CN 201010575745A CN 201010575745 A CN201010575745 A CN 201010575745A CN 101985714 B CN101985714 B CN 101985714B
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magnesium
master alloy
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aluminium
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CN101985714A (en
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王慧远
姜启川
肖为
南小龙
王珵
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Jilin University
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Abstract

The invention relates to the field of metal materials, in particular to a high-plasticity magnesium alloy and a preparation method thereof. The alloy comprises the following chemical components in percentage by mass: 0.1 to 6.0 percent of aluminum, 0.1 to 3.0 percent of tin, 0.01 to 2.0 percent of manganese, 0.01 to 2.0 percent of strontium and the balance of magnesium and other inevitable impurities; simultaneously, the magnesium alloy can also contain one or more of additional elements such as zinc and stibium and rare earth elements. The preparation method comprises the following steps of: melting the magnesium and the aluminum, adding the tin, the additional elements, the rare earth elements and the strontium in turn, stirring and refining, and preparing a melt into a plate by a cast-rolling and rolling process; or directly pouring the melt into a cast ingot; or pouring the melt into the cast ingot, extruding the cast ingot into a section or a thick plate and rolling the thick plate into a thin plate. The preparation method enhances the intensity and toughness of the alloy and overcomes the defects that a cast magnesium alloy is difficult to adapt to a deformation condition and a deformed magnesium alloy is difficult to adapt to a casting condition.

Description

A kind of high plastic magnesium alloy and preparation method thereof
Technical field
The present invention relates to metal material field, particularly relate to a kind of high plastic magnesium alloy and preparation method thereof.
Background technology
Magnesiumalloy has the special performance of many excellences, like high specific strength, electric-conductivity heat-conductivity high property as the lightest engineering structure metallic substance; High damping shock absorption property; High electrostatic shielding property has good advantages such as regeneration concurrently, in field selections such as Aeronautics and Astronautics, automobile and communication, enjoys favor.Especially aspect lightweight, has the alternate of being difficult to significant advantage.Yet because the crystal of magnesium is a close-packed hexagonal structure, slip system is few, and plastic deformation ability is poor, becomes one of important bottleneck problem of restriction magnesiumalloy development.Thereby exploration and development of new high plastic magnesium alloy are this hot research fields all the time.
Yet the existing magnesiumalloy trade mark is still less, and cast magnesium alloys such as AZ91 etc. are difficult to be out of shape operating mode usually, and the performance of wrought magnesium alloys such as AZ31 is difficult to be suitable for casting operating mode equally.Thereby, develop a kind of novel magnesium alloy that not only had been suitable for casting but also had been fit to the distortion operating mode and have great importance.
Summary of the invention
It is simple, reliable to the purpose of this invention is to provide a kind of technology; And high plastic magnesium alloy that is easy to apply and preparation method thereof; This alloy both had been applicable to that casting operating mode directly uses, and was suitable for being out of shape operating mode again, like rolled plate, extruded tube, extruded section etc.
Technical scheme of the present invention is: the aluminium of magnesium ingot and required adding is melted together; Add tin then, add required interpolation element and REE again, introduce manganese through aluminium-manganese or magnesium-manganese master alloy again after stirring; Carry out deironing and sila matter; Add aluminium-strontium or magnesium-strontium master alloy then and introduce strontium, stir at last, refining treatment, melt is processed sheet material through casting and rolling technology after waiting to leave standstill insulation; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab, again heavy plate rolling is become thin plate.
Specifically comprise:
1. a high plastic magnesium alloy is characterized in that, the chemical ingredients mass percent of this magnesiumalloy is: aluminium 0.1-6.0, and tin 0.1-3.0, manganese 0.01-2.0, strontium 0.01-2.0, all the other are magnesium and unavoidable impurities; Simultaneously, this magnesiumalloy also contains one or more in interpolation element zinc, antimony and the REE.
2. high plastic magnesium alloy according to claim 1 is characterized in that, described chemical ingredients mass percent is: aluminium 1.80-2.95, tin 1.00-2.95, manganese 0.05-0.55, strontium 0.01-1.10;
3. high plastic magnesium alloy according to claim 1 is characterized in that, described interpolation constituent content mass percent is: zinc 0-1.0, antimony 0-3.0;
4. high plastic magnesium alloy according to claim 1 is characterized in that, described REE is one or more in neodymium, lanthanum, yttrium, the cerium, and the content mass percent of REE is: 0-2.0;
5. a preparation method who is used for the described high plastic magnesium alloy of claim 1 is characterized in that, this method may further comprise the steps:
(1) gets the raw materials ready according to above-mentioned magnesiumalloy component content; Comprise pure magnesium, fine aluminium, pure tin, aluminium-manganese or magnesium-manganese master alloy, aluminium-strontium or magnesium-strontium master alloy, pure zinc, star antimony, magnesium-neodymium master alloy, magnesium-lanthanum master alloy, magnesium-yttrium master alloy, magnesium-cerium master alloy; The master alloy that is adopted is the commercial criterion master alloy, and the alloying element mass percentage content is 10-15;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively with in one or more adding melts in above-mentioned content and the pure zinc process preheating, star antimony, magnesium-neodymium master alloy, magnesium-lanthanum master alloy, magnesium-yttrium master alloy, the magnesium-cerium master alloy; The adding mode is that the top fusing drenches mode, stirs;
(5) aluminium-manganese or the magnesium-manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) aluminium-strontium or the magnesium-strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.
The present invention compares with present prior art has following characteristics:
Alloy of the present invention both had been applicable to the casting operating mode, was suitable for being out of shape operating mode again, like rolled plate, extruded tube, extruded section etc.; And preparation technology is simple, is easy to apply.
1) magnesiumalloy of the present invention has high-ductility, and it is that 20-43%, tensile strength are that 210-280MPa, rolling deformation rate can reach 87% that the alloy behind the optimizing components can obtain unit elongation, once depresses deflection greater than 50%;
2) alloy of the present invention does not contain and has toxic lead element, does not contain to cause brittle element silicon yet;
3) add aluminium, tin, manganese and strontium element simultaneously in the alloy of the present invention, both improved the intensity of alloy, improved obdurability again; Add tin and can also play reduction alloy stacking fault energy, thereby improve plasticity; After adding manganese element, can also play the effect of removing iron and sila matter, improve the alloy purity, simultaneously, manganese can also crystal grain thinning; After adding strontium element, also can play the effect that purifies crystal boundary, refined cast structure and recrystallized structure, in addition, strontium can also play and improve precipitated phase Mg 17Al 12And Mg 2The effect of Sn;
4) alloy of the present invention and the alloy phase ratio that does not add manganese element, when improving plasticity, the corrosion resistance nature and the anti-fatigue performance of alloy are significantly improved;
5) interpolation element zinc, antimony and the rear earth element nd in the alloy of the present invention, lanthanum, yttrium, cerium also can play grain refining and fire-retardant effect, help improving the performance of alloy.
6) characteristics of this patent on the preparation method are: earlier magnesium ingot and aluminium are melted simultaneously, add required interpolation element zinc, antimony and rear earth element nd, lanthanum, yttrium, cerium then; Introduce manganese again, deironing and sila matter; Introduce strontium at last.
Embodiment
Embodiment one
(1) press the mass percent of element in the alloy: aluminium 2.95%, tin 2.85%, manganese 0.15%, strontium 0.18%, all the other are magnesium, take by weighing in the middle of required pure magnesium, fine aluminium, pure tin, aluminium-10% manganese, aluminium-10% strontium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) aluminium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) aluminium-10% strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.It is that 30-43%, tensile strength are that 210-250MPa, rolling deformation rate can reach 87% that this alloy can obtain unit elongation, once depresses deflection greater than 50%, and the alloy when alloy corrosion resistance can more not add manganese and strontium improves more than 50%.
Embodiment two
(1) press the mass percent of element in the alloy: aluminium 5.85%, tin 2.65%, manganese 0.02%, strontium 0.03%, all the other are magnesium, take by weighing required fine aluminium, pure tin, magnesium-10% manganese master alloy, magnesium-15% strontium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) magnesium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) magnesium-15% strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is directly poured into ingot casting; Or pour into ingot casting earlier, then ingot casting is squeezed into section bar or slab at the 250-450 degree.It is that 20-25%, tensile strength are 250-280MPa that this alloy can obtain unit elongation, and the alloy when alloy corrosion resistance can more not add manganese and strontium improves more than 50%.
Embodiment three
(1) presses the mass percent of element in the alloy: aluminium 1.65%, tin 0.85%, manganese 1.85%, strontium 1.45%; Add element: zinc 0.95, antimony 2.7%; All the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, magnesium-10% manganese master alloy, aluminium-10% strontium master alloy, pure zinc, star antimony;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with above-mentioned content and add in the melt through the pure tin of preheating, pure zinc, star antimony, the adding mode is that the top fusing drenches mode;
(4) magnesium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(5) aluminium-10% strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(6) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(7) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.
Embodiment four
(1) presses the mass percent of element in the alloy: aluminium 4.25%, tin 1.95%; Manganese 0.85%; Strontium 0.95%; Zinc 0.55, neodymium 0.1%, yttrium 1.5%, all the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, pure zinc, magnesium-10% manganese master alloy, magnesium-15% strontium master alloy, magnesium-10% neodymium master alloy, magnesium-12% yttrium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively above-mentioned content and pure zinc, magnesium-10% neodymium master alloy, magnesium-12% yttrium master alloy the process preheating are added in the melt, the adding mode is that the top fusing drenches mode, stirs;
(5) magnesium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) magnesium-15% strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.It is that 20-30%, tensile strength are 230-270MPa that this alloy can obtain unit elongation.
Embodiment five
(1) presses the mass percent of element in the alloy: aluminium 1.55%, tin 2.55%, manganese 1.25%, strontium 0.55%; Antimony 1.25, neodymium 1.45%, lanthanum 1.25%, cerium 1.35%; All the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, star antimony, magnesium-10% manganese master alloy, aluminium-10% strontium master alloy, magnesium-10% neodymium master alloy, magnesium-10% lanthanum master alloy, magnesium-15% cerium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively above-mentioned content and star antimony, magnesium-10% neodymium master alloy, magnesium-10% lanthanum master alloy, magnesium-15% cerium master alloy the process preheating are added in the melt, the adding mode is that the top fusing drenches mode, stirs;
(5) magnesium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) aluminium-10% strontium alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.
Embodiment six
(1) presses the mass percent of element in the alloy: aluminium 3.25%, tin 0.55%, manganese 1.25%, strontium 0.55%; Antimony 1.25%, neodymium 1.55%, lanthanum 0.25%, cerium 0.05%; All the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, magnesium-10% manganese master alloy, magnesium-10% strontium master alloy, star antimony, magnesium-10% neodymium master alloy, magnesium-10% lanthanum master alloy, magnesium-15% cerium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively above-mentioned content and star antimony, magnesium-10% neodymium master alloy, magnesium-10% lanthanum master alloy, magnesium-15% cerium master alloy the process preheating are added in the melt, the adding mode is that the top fusing drenches mode, stirs;
(5) magnesium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) magnesium-10% strontium master alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.
Embodiment seven
(1) presses the mass percent of element in the alloy: aluminium 2.55%, tin 1.50%, manganese 0.35%, strontium 0.80%, zinc 0.15, lanthanum 1.45%; All the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, aluminium-10% manganese, aluminium-10% strontium master alloy, pure zinc, the magnesium-10% lanthanum master alloy of comprising;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively above-mentioned content and pure zinc, magnesium-10% lanthanum master alloy the process preheating are added in the melt, the adding mode is that the top fusing drenches mode, stirs;
(5) aluminium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) aluminium-10% strontium alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.It is that 25-30%, tensile strength are 210-240MPa that this alloy can obtain unit elongation.
Embodiment eight
(1) presses the mass percent of element in the alloy: aluminium 2.75%, tin 2.80%, manganese 0.04%, strontium 0.25%, zinc 0.45%, cerium 0.05%; All the other are magnesium, take by weighing required pure magnesium, fine aluminium, pure tin, aluminium-10% manganese master alloy, aluminium-10% strontium master alloy, pure zinc, magnesium-15% cerium master alloy;
(2) evenly spread No. two solvents of one deck in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread No. two solvents of one deck topmost at last, carry out heat fused;
(3) with in above-mentioned content and the pure tin adding melt through preheating, the adding mode is that the top fusing drenches mode;
(4) respectively above-mentioned content and pure zinc, magnesium-15% cerium master alloy the process preheating are added in the melt, the adding mode is that the top fusing drenches mode, stirs;
(5) aluminium-10% manganese master alloy through preheating with above-mentioned content adds in the melt, and the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) aluminium-10% strontium alloy through preheating with above-mentioned content adds in the melt, stirs;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at the 250-450 degree, again heavy plate rolling is become thin plate.

Claims (3)

1. a high plastic magnesium alloy is characterized in that, the chemical ingredients mass percent of this magnesiumalloy is: aluminium 0.1-4.25, and tin 2.55-3.0, manganese 0.85-2.0, strontium 0.55-2.0, all the other are magnesium and unavoidable impurities; Simultaneously, this magnesiumalloy also contains one or more in interpolation element zinc, antimony and the REE;
Described high plastic magnesium alloy prepares through following steps:
(1) gets the raw materials ready: comprise pure magnesium, fine aluminium, pure tin, aluminium-manganese or magnesium-manganese master alloy, aluminium-strontium or magnesium-strontium master alloy, pure zinc, star antimony, magnesium-neodymium master alloy, magnesium-lanthanum master alloy, magnesium-yttrium master alloy, magnesium-cerium master alloy; The master alloy that is adopted is the commercial criterion master alloy, and manganese, strontium, neodymium, lanthanum, yttrium, cerium alloy element mass percentage content are 10-15 in said master alloy;
(2) evenly spread one deck barium fluxing agent in crucible bottom earlier, add pure magnesium ingot, on magnesium ingot, add required aluminium ingot then, spread one deck barium fluxing agent topmost at last, carry out heat fused;
(3) will pass through in the pure tin adding melt of preheating, the adding mode is that the top fusing drenches mode;
(4) will pass through in the pure zinc, star antimony, magnesium-neodymium master alloy, magnesium-lanthanum master alloy, magnesium-yttrium master alloy, magnesium-cerium master alloy of preheating one or more respectively and add in melts, the adding mode is that the top fusing drenches mode, stirs;
(5) will pass through in the aluminium-manganese or magnesium-manganese master alloy adding melt of preheating, the adding mode is that the top fusing drenches mode, stirs, and carries out deironing and sila matter;
(6) will pass through in the aluminium-strontium or magnesium-strontium master alloy adding melt of preheating, stir;
(7) keep temperature to be lower than below 820 ℃, add barium fluxing agent, stir, and carry out the blowing argon gas refining from the bottom;
(8) leave standstill processing, treat that temperature reduces to below 750 ℃, melt is processed the sheet material of 0.2-10 millimeter thickness through casting and rolling technology; Or melt directly poured into ingot casting; Or pour into ingot casting earlier, and then ingot casting is squeezed into section bar or slab at 250-450 degree centigrade, again heavy plate rolling is become thin plate.
2. high plastic magnesium alloy according to claim 1 is characterized in that, described interpolation constituent content mass percent is: zinc 0-1.0, antimony 0-3.0.
3. a kind of high plastic magnesium alloy according to claim 1 and 2 is characterized in that, described REE is one or more in neodymium, lanthanum, yttrium, the cerium, and the content mass percent of REE is: 0-2.0.
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