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 PDFInfo
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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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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 87
- 239000000956 alloy Substances 0.000 title claims abstract description 87
- 239000011777 magnesium Substances 0.000 title claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 24
- -1 magnesium rare earth Chemical class 0.000 title claims abstract description 17
- 239000006104 solid solution Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910018503 SF6 Inorganic materials 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960000909 sulfur hexafluoride Drugs 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000004080 punching Methods 0.000 claims description 14
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 229910000831 Steel Inorganic materials 0.000 abstract 2
- 239000010959 steel Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910000861 Mg alloy Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
一种室温高韧性单相固溶体镁稀土基合金，其化学成分为Mg-xRE-y(Zn+Sc)-z(Ag+Zr).其中0.5≤x≤3.0，0.1≤y≤1.5，0.01≤z≤1.0（wt.%），稀土元素包括Gd、Y、Dy、Er、Tm和Lu；其制备方法主要是，将上述原料加入自动控温电阻炉中，采用六氟化硫和氩气混合气体保护，熔炼温度为680-800℃，在650-770℃浇注到钢模中，钢模要在500-600℃下充分预热，浇注后，在650-750℃炉中保温30-120分钟，然后用水冷却至室温。本发明的单相固溶体镁稀土基合金晶粒尺寸小，延展性好，室温延伸率超过20%，力学性能和加工性能优良，耐腐蚀性能优异。A room temperature high toughness single-phase solid solution magnesium rare earth alloy, its chemical composition is Mg-xRE-y(Zn+Sc)-z(Ag+Zr) . Wherein 0.5≤x≤3.0, 0.1≤y≤1.5, 0.01≤ z≤1.0 (wt.%), rare earth elements include Gd, Y, Dy, Er, Tm and Lu; its preparation method is mainly to add the above raw materials into an automatic temperature-controlled resistance furnace, and use sulfur hexafluoride and argon to mix Gas protection, the melting temperature is 680-800°C, pouring into the steel mold at 650-770°C, the steel mold should be fully preheated at 500-600°C, after pouring, keep it in a furnace at 650-750°C for 30-120 minutes , and then cooled to room temperature with water. The single-phase solid solution magnesium rare earth-based alloy of the invention has small grain size, good ductility, elongation at room temperature exceeding 20%, excellent mechanical properties and processing properties, and excellent corrosion resistance.
Description
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
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.
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| 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 | A kind of high toughness biomedical magnesium alloy and preparation method thereof |
| CN112779446B (en) * | 2020-12-26 | 2022-07-15 | 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-rare earth-zirconium-based magnesium-based alloy and preparation method thereof |
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| 余琨等.铸造Mg-Re-Zn-Zr合金的组织和性能.《特种铸造及有色合金》.2001,(第6期),第6-8页. * |
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