CN102277521B - High-temperature high-tenacity single-phase solid-solution magnesium rare earth base alloy and preparation method thereof - Google Patents

High-temperature high-tenacity single-phase solid-solution magnesium rare earth base alloy and preparation method thereof Download PDF

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CN102277521B
CN102277521B CN 201110228615 CN201110228615A CN102277521B CN 102277521 B CN102277521 B CN 102277521B CN 201110228615 CN201110228615 CN 201110228615 CN 201110228615 A CN201110228615 A CN 201110228615A CN 102277521 B CN102277521 B CN 102277521B
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ingot
alloy
rare earth
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room temperature
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CN102277521A (en
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彭秋明
朱键卓
田永君
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Yanshan University
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Yanshan University
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Abstract

The invention relates to a high-temperature single-phase solid-solution magnesium rare earth base alloy of which the chemical composition is Mg-xRE-y(Zn+Sc)-z(Ag+Zr), wherein x is more than or equal to 0.5 and less than or equal to 3.0, y is more than or equal to 0.1 and less than or equal to 1.5, z is more than or equal to 0.01 and less than or equal to 1.0 (wt%), and rare earth elements comprise Gd, Y, Dy, Er, Tm and Lu. A preparation method mainly comprises the following steps of: adding the raw materials into an automatic temperature-controlled resistance furnace, protecting the raw materials by using a mixed gas of sulfur hexafluoride and argon, smelting the raw materials at the temperature of 680-800 DEG C, pouring the melt in a steel mold at the temperature of 650-770 DEG C, fully preheating the steel mold at the temperature of 500-600 DEG C, insulating the steel mold in a 650-750 DEG C furnace for 30-120 min after pouring, and cooling the steel mold by using water to room temperature. The single-phase solid-solution magnesium rare earth base alloy provided by the invention has small grain size, good ductility, room temperature elongation coefficient exceeding 20%, excellent mechanical properties and processing properties and excellent corrosion resistance.

Description

Room temperature high tenacity single phase solid solution magnesium rare earth based alloy and preparation method
Technical field
The present invention relates to a kind of metallic substance and preparation method thereof, particularly a kind of magnesium alloy and preparation method thereof.
Background technology
Magnesium alloy has that light specific gravity, specific tenacity and specific rigidity are high, damping and amortization and machinability is good, thermal conductivity is good, the electromagnetic shielding ability strong and vibration damping is good and be easy to reclaim advantage, satisfy Aeronautics and Astronautics, modern automobile industry to loss of weight, energy-conservation requirement, be described as " green engineering material of 21 century ".
Wrought magnesium alloys mainly contains magnalium system at present, magnesium zinc system and magnesium rare earth-based alloy.The magnesium aluminum series alloy is to be most commonly used to the distortion system, and still, this class alloy has very strong basal plane texture, significant asymmetry and relative narrow processing temperature scope.Because 437 ℃ of the eutectic temperatures of magnalium, hot processing temperature is usually less than 350 ℃, and therefore, the speed of distortion is lower, and the products production cost is high.On the other hand, if select high temperature (above 350 ℃), the eutectic phase dissolving, cause alloy hot tearing and surface quality to reduce [K.U. Kainer, Magnesium Alloys and Technologies, WILEY-VCH Verlag GmbH, Weiheim, 2003].Magnesium zinc system is not because contain aluminium, its tissue can pass through to add the effective refinement of Zr, yet this class alloy is easy to form the casting micropore, Hot Cracking is obvious in the operation of rolling, be difficult to welding, so this class alloy application in deformable material also seldom [H.E. Friedrich, B. L.Mordike, Magnesium Technology, Springer Press, Berlin, 2006].Compare with top two kinds, the performance of magnesium rare earth-based alloy is more outstanding, such as WE43(Mg-4.1Y-2.2Nd-1HRE-0.5Zr) and WE54(Mg-5.2Y-1.7Nd-1.7HRE-0.4Zr) alloy has good mechanical property and thermostability, but this class alloy is along with the increase of content of rare earth, the price of alloy obviously rises, and the more important thing is, along with the increase of content of rare earth, the amount showed increased of second phase particles, the corrosion resistance nature of alloy sharply descends.Therefore, develop the novel good deformation performance that has, the alloy of excellent corrosion resistance is to the application of magnesium alloy very necessary [F. Czerwinski, Magnesium injection molding, Springer press, Bolton, 2007].
Summary of the invention
The object of the present invention is to provide a kind of room temperature high tenacity single phase solid solution magnesium rare earth based alloy and preparation method with good deformation performance and excellent corrosion resistance.The present invention improves alloy mechanical property by solution strengthening and refined crystalline strengthening.
The chemical composition of magnesium rare earth based alloy of the present invention is Mg-xRE-y (Zn+Sc)-z (Ag+Zr), and wherein, x, y, z are mass percent (wt.%), 0.5%≤x≤3.0%, 0.1%≤y≤1.5%, 0.01%≤z≤1.0%; RE is rare earth element, comprises two or more of Gd, Y, Dy, Er, Tm and Lu, and the massfraction ratio of various rare earth elements equates among the RE; (Zn+Sc) one or both among expression Zn and the Sc, when adding two kinds of elements simultaneously, the massfraction of each element is than equating; (Ag+Zr) one or both among expression Ag and the Zr, when adding two kinds of elements simultaneously, the massfraction of each element is than equating; Surplus is Mg.
The preparation method of above-mentioned magnesium rare earth based alloy:
(1) raw material: the Mg ingot of quality purity 99.5%, 99.9% Zn ingot, 99.99% Ag ingot, 99% Sc ingot, 99% Mg-20wt.%RE master alloy and 99% Mg-33.3 wt.%Zr master alloy are raw material.
(2) reinforced: as first above-mentioned ingot metal and intermediate alloy ingot to be removed surface scale; intermediate alloy ingot is wanted first 200-400 ℃ of abundant preheating; then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Sc ingot, Ag ingot and Mg-Zr intermediate alloy ingot are added in the temperature automatically controlled resistance furnace in order; adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected; a kind of raw material of every interpolation stirred 10 minutes.
(3) melting: smelting temperature is 680-800 ℃, all raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 650-770 ℃, punching block will be 500-600 ℃ of lower abundant preheating, and after the cast, insulation is 30-120 minute in 650-750 ℃ of stove, then with being water-cooled to room temperature, obtains a kind of room temperature high tenacity single phase solid solution magnesium rare earth based alloy.
The present invention compared with prior art has following advantage:
1, changes the lattice parameter of alloy by adding the appropriate alloy element, eliminate the anisotropy of alloy, put forward heavy alloyed deformation processing performance.
2, because all alloy elements all distribute with the solid solution attitude, fundamentally eliminate second-phase, eliminated the effect of alloy micro-cell corrosion, improved the corrosion resistance nature of alloy.
3, alloy of the present invention is comprised of single phase solid solution, and grain-size is little, and room temperature ductility is good, the room temperature unit elongation surpasses 20%, mechanical property and processing characteristics are outstanding, and excellent anti-corrosion performance has broad application prospects at high-performance deformation material and bio-medical field.
Description of drawings
Fig. 1 is the metallographic structure figure of the embodiment of the invention 1 Mg-0.5RE-1.5Sc-0.01Ag alloy.
Fig. 2 is the Electronic Speculum figure after corrosion treatment of the embodiment of the invention 1 Mg-0.5RE-1.5Sc-0.01Ag alloy.
Fig. 3 is the room-temperature mechanical property figure of Mg-2RE-1Zn-0.2Ag-0.2Zr alloy and AZ31 in the embodiment of the invention 2.
As can be seen from Figure 1 the alloy grain through the present invention's preparation is little, is evenly distributed; As can be seen from Figure 2, alloy mainly is uniform corrosion in solvent, has basically eliminated pitting attack, thereby has improved the solidity to corrosion of whole alloy; As can be seen from Figure 3, compare with best wrought magnesium alloys AZ31 solid solution alloy in the present magnesium alloy, the distortion of Mg-2RE-1Zn-0.2Ag-0.2Zr alloy is more even, and unit elongation obviously improves.
Embodiment
Embodiment 1
According to Mg-0.5RE-1.5Sc-0.01Ag(wt.%) composition carry out raw material mass mixture ratio, magnesium is surplus, wherein the Gd among the RE, Y, Dy, Er and Tm massfraction are than equating, the quality purity of all raw materials is respectively: 99.5% Mg ingot, 99% Mg-20wt.%RE intermediate alloy ingot, 99% Sc ingot and 99.99% Ag ingot.First above-mentioned ingot metal and intermediate alloy ingot are removed surface scale, intermediate alloy ingot is wanted first 200 ℃ of abundant preheatings, then successively metal M g ingot, Mg-RE intermediate alloy ingot, Sc ingot and Ag ingot are added in the temperature automatically controlled resistance furnace in order, smelting temperature is 700 ℃, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes; All raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 770 ℃, punching block will be 500 ℃ of lower preheatings, and after the cast, insulation is 120 minutes in 650 ℃ of stoves, then with being water-cooled to room temperature, obtains room temperature high tenacity single phase solid solution magnesium rare earth based alloy.The room temperature unit elongation of this alloy surpasses 20%.
Embodiment 2:
According to Mg-2RE-1Zn-0.2Ag-0.2Zr(wt.%) form and carry out raw material mass mixture ratio, magnesium is surplus.Wherein the Gd among the RE, Y and Lu massfraction are than equating, the quality purity of all raw materials is respectively: 99.5% Mg ingot, 99% Mg-20wt.%RE intermediate alloy ingot, 99.9% Zn ingot, 99.99% Ag ingot and 99% Mg-33.3wt.%Zr intermediate alloy ingot.First above-mentioned ingot metal and intermediate alloy ingot are removed surface scale, intermediate alloy ingot is wanted first 400 ℃ of abundant preheatings, then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Ag ingot and Mg-Zr intermediate alloy ingot are added in the temperature automatically controlled resistance furnace in order, smelting temperature is 680 ℃, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes; All raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 650 ℃, punching block will be 600 ℃ of lower preheatings, and after the cast, insulation is 30 minutes in 750 ℃ of stoves, then with being water-cooled to room temperature, obtains room temperature high tenacity single phase solid solution magnesium rare earth based alloy.The room temperature unit elongation of this alloy surpasses 20%.
Embodiment 3
Carry out raw material mass mixture ratio according to the Mg-3RE-0.1Zn-0.05Ag-0.05Zr composition, magnesium is surplus.Wherein the Gd among the RE, Y massfraction are than equating, the quality purity of all raw materials is respectively: 99.5% Mg ingot, 99% Mg-20wt.%RE intermediate alloy ingot, 99.9% Zn ingot, 99.99% Ag ingot and 99% Mg-33.3wt.%Zr intermediate alloy ingot.First above-mentioned ingot metal and intermediate alloy ingot are removed surface scale, intermediate alloy ingot is wanted first 250 ℃ of abundant preheatings, then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Ag ingot and Mg-Zr intermediate alloy ingot are added in the temperature automatically controlled resistance furnace in order, smelting temperature is 750 ℃, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes; All raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 660 ℃, punching block will be 580 ℃ of lower preheatings, and after the cast, insulation is 100 minutes in 680 ℃ of stoves, then with being water-cooled to room temperature, obtains room temperature high tenacity single phase solid solution magnesium rare earth based alloy.The room temperature unit elongation of this alloy surpasses 20%.
Embodiment 4
Carry out raw material mass mixture ratio according to the Mg-2.4RE-0.5Zn-0.5Sc-0.5Zr composition, magnesium is surplus.Wherein the Gd among the RE, Y, Dy and Tm massfraction are than equating, the quality purity of all raw materials is respectively: 99.5% Mg ingot, 99% Mg-20wt.%RE intermediate alloy ingot, 99.9% Zn ingot, 99% Sc ingot and 99% Mg-33.3wt.%Zr intermediate alloy ingot.First above-mentioned ingot metal and intermediate alloy ingot are removed surface scale, intermediate alloy ingot is wanted first 300 ℃ of abundant preheatings, then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Sc ingot and Mg-Zr intermediate alloy ingot are added in the temperature automatically controlled resistance furnace in order, smelting temperature is 770 ℃, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes; All raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 720 ℃, punching block will be 590 ℃ of lower preheatings, and after the cast, insulation is 90 minutes in 700 ℃ of stoves, then with being water-cooled to room temperature, obtains room temperature high tenacity single phase solid solution magnesium rare earth based alloy.The room temperature unit elongation of this alloy surpasses 20%.
Embodiment 5
Carry out raw material mass mixture ratio according to Mg-2.4RE-0.5Zn-0.5Sc-0.05 Ag composition, magnesium is surplus.Wherein the Gd among the RE, Y, Dy, Er, Tm and Lu massfraction are than equating, the quality purity of all raw materials is respectively: 99.5% Mg ingot, 99% Mg-20wt.%RE intermediate alloy ingot, 99.9% Zn ingot, 99% Sc ingot and 99.99% Ag ingot.First above-mentioned ingot metal and intermediate alloy ingot are removed surface scale, intermediate alloy ingot is wanted first 350 ℃ of abundant preheatings, then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Sc ingot and Ag ingot are added in the temperature automatically controlled resistance furnace in order, smelting temperature is 800 ℃, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes; All raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 700 ℃, punching block will be 550 ℃ of lower preheatings, and after the cast, insulation is 60 minutes in 720 ℃ of stoves, then with being water-cooled to room temperature, obtains room temperature high tenacity single phase solid solution magnesium rare earth based alloy.The room temperature unit elongation of this alloy surpasses 20%.
Table 1 is alloy mechanical property at room temperature

Claims (2)

1. a room temperature high tenacity single phase solid solution magnesium rare earth based alloy is characterized in that, its chemical composition is Mg-xRE-y (Zn+Sc)-z (Ag+Zr), wherein, x, y, z are mass percent wt.%, 0.5%≤x≤3.0%, 0.1%≤y≤1.5%, 0.01%≤z≤1.0%; RE is rare earth element, comprises two or more of Gd, Y, Dy, Er, Tm and Lu, and the massfraction ratio of various rare earth elements equates among the RE; Zn+Sc, one or both among expression Zn and the Sc, when adding two kinds of elements simultaneously, the massfraction of each element is than equating; Ag+Zr represents one or both among Ag and the Zr, and when adding two kinds of elements simultaneously, the massfraction of each element is than equating.
2. the preparation method of the single phase solid solution magnesium rare earth based alloy of the claims 1 is characterized in that:
(1) raw material: the Mg ingot of quality purity 99.5%, 99.9% Zn ingot, 99.99% Ag ingot, 99% Sc ingot, 99% Mg-20wt.%RE master alloy and 99% Mg-33.3 wt.%Zr master alloy are raw material;
(2) reinforced: as first above-mentioned ingot metal and intermediate alloy ingot to be removed surface scale, intermediate alloy ingot is wanted first 200-400 ℃ of abundant preheating, then successively metal M g ingot, Zn ingot, Mg-RE intermediate alloy ingot, Sc ingot, Ag ingot and Mg-Zr intermediate alloy ingot are added in the temperature automatically controlled resistance furnace in order, adopt sulfur hexafluoride and argon gas 1:19 mixed gas protected, a kind of raw material of every interpolation stirred 10 minutes;
(3) melting: smelting temperature is 680-800 ℃, all raw materials all add finish after, restir 30 minutes; Be poured in the punching block at 650-770 ℃, punching block will be 500-600 ℃ of lower abundant preheating, and after the cast, insulation is 30-120 minute in 650-750 ℃ of stove, then with being water-cooled to room temperature.
CN 201110228615 2011-08-11 2011-08-11 High-temperature high-tenacity single-phase solid-solution magnesium rare earth base alloy and preparation method thereof Expired - Fee Related CN102277521B (en)

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CN104195483B (en) * 2014-08-19 2016-06-01 中国科学院金属研究所 A kind of thermal treatment process improving Mg-Zn-Y-Zr corrosion resistance of magnesium alloy
CN105803282B (en) * 2016-03-22 2017-12-08 中国兵器科学研究院宁波分院 A kind of single-phase Multielement rare-earth magnesium alloy biodegradation material and preparation method thereof
CN109457130B (en) * 2019-01-14 2020-11-20 兰州理工大学 High-toughness biomedical magnesium alloy and preparation method thereof
CN112779446A (en) * 2020-12-26 2021-05-11 中国科学院长春应用化学研究所 Multi-element microalloyed high-strength heat-resistant rare earth magnesium alloy and preparation method thereof

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CN101200784A (en) * 2007-12-17 2008-06-18 中国科学院长春应用化学研究所 Magnesium-zinc-lanthanon-zirconium magnesium alloy and method for preparing same

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CN101200784A (en) * 2007-12-17 2008-06-18 中国科学院长春应用化学研究所 Magnesium-zinc-lanthanon-zirconium magnesium alloy and method for preparing same

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