CN101255518A - High-strength antirusting Mg-Al-Mn die-casting magnesium alloy containing yttrium-rich rare earth - Google Patents
High-strength antirusting Mg-Al-Mn die-casting magnesium alloy containing yttrium-rich rare earth Download PDFInfo
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Abstract
The invention relates to a high-strength erosion-resistant die cast magnesium alloy containing yttrium-rich rare earth. The alloy is prepared by 97% to 91% by mass percentage of AM60 magnesium alloy and 3% to 9% by mass percentage of magnesium- yttrium-rich interalloy; the magnesium- yttrium-rich interalloy is prepared by 80% by mass percentage of magnesium and 20% by mass percentage of special yttrium-rich rare earth; the special yttrium-rich rare earth is the residual cheap yttrium-rich rare earth after Eu, Dy, Tb and Lu high-valence elements is extracted from common yttrium-rich rare earth; by adding some special yttrium-rich mixing rare earth to AM60 alloy, the high plasticity of the alloy is maintained, the strength and corrosion resistance is improved, the comprehensive performance is obviously enhanced compared with AM60 magnesium alloy.
Description
Technical field
The present invention relates to a kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains, belong to the class of metal materials field.
Background technology
Under the exhausted day by day situation of current mineral metal products resource, magnesium comes into one's own with its aboundresources, and the demand of structural timber lightweight, environmental protection and energy saving problem has stimulated the magnesium industry focus that becomes international more.Yet traditional magnesium alloy (as the AM60 magnesium alloy etc.) because the shortcoming of proper property differences such as intensity, corrosion resistance nature can't satisfy the requirement in fields such as using vehicle, defence and military, aerospace.Studies show that: rare earth element can improve the mechanical property and the corrosion resisting property of magnesium alloy as alloy element, thereby is introduced in the middle of the magnesium alloy.
It is common rich yttrium mixed rare earth that magnesium alloy uses one of maximum mishmetal at present, and main component is Y, Ho, Er, also comprises high price elements such as Eu, Dy, Tb, Lu.Because market and industry need, after the extraction high valence elements, the yttrium-rich RE that has remained a large amount of cheapnesss can not be fully used from rich yttrium raw material at present.Open up the approach that utilizes of this yttrium-rich RE, significant to the comprehensive utilization and the balanced growth of rare earth resources, the performance that improves magnesium alloy materials also there is significance.
Utilization separates the yttrium-rich RE after the high valence elements, on the basis of AM60 magnesium alloy, improve intensity, unit elongation and the corrosion resisting property of alloy, bring into play its advantage, develop the novel high-strength corrosion-resistant magnesium alloy, both promoted the performance of magnesium alloy materials, help solving the yttrium-rich RE resource of separating behind the high price rare earth again and overstock problem in a large number, the product of alleviating resource needs contradiction, the unbalanced present situation of production and marketing.
Summary of the invention
The present invention is directed to that present AM60 diecast magnesium alloy intensity is low, the weak link of corrosion-resistant, the high-strength and high ductility Mg-Al-Mn that contains yttrium-rich RE is provided diecast magnesium alloy.On the basis of AM60 alloy, by adding a certain amount of special rich yttrium mixed rare earth, both having kept this is the high advantage of alloy plasticity, improve the intensity and the erosion resistance of alloy again, its over-all properties has been compared with the AM60 magnesium alloy more significantly and has been improved, and can satisfy the requirement that industrial development improves constantly magnesium alloy.
A kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains of the present invention, its composition is 5.7%～6.3% for Al by mass percentage, Mn is 0.27%～0.4%, and Y is 0.3%～1.5%, and Er is 0.1%～0.15%, Ho is 0.05%～0.1%, impurity element Fe≤0.02%, Cu≤0.002%, Si≤0.01%, Ni≤0.001%, surplus are magnesium; Described alloy is that 97%～91% AM60 magnesium alloy and mass percent are that magnesium-Fu yttrium master alloy of 3%～9% is made by mass percent; Described magnesium-Fu yttrium master alloy is to be that 80% magnesium and mass ratio are that 20% special yttrium-rich RE is made by mass ratio; Described special yttrium-rich RE is a remaining cheap yttrium-rich RE behind common yttrium-rich RE extraction Eu, Dy, the high price elements such as Tb, Lu, and special yttrium-rich RE chemical constitution is Y:70%～90% by mass percentage, Er:5%～20%, Ho:1%～10%.
On the preparation method, the present invention's alloy is different from traditional magnesium alloy part and is: make magnesium-Fu yttrium master alloy earlier, add magnesium-Fu yttrium master alloy again in fusion process.This technological process middle-weight rare earths loss is few, is easy to composition, and smelting time shortens, thereby has promoted the alloy quality, reduces manufacturing cost.
The preparation method who contains the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy of the present invention:
(1), be that 80% magnesium ingot and quality proportioning are that 20% rich yttrium mixed rare earth is a raw material by the quality proportioning, magnesium ingot and rich yttrium mixed rare earth raw material are put into cast iron or plumbago crucible heat fused and be warming up to 780 ℃, be cast into magnesium-Fu yttrium master alloy after stirring; Feed SF in the fusion process
6: CO
2Volume ratio is 1: 200 a shielding gas; described rich yttrium mixed rare earth is the yttrium-rich RE after common yttrium-rich RE extracts high price elements such as Eu, Dy, Tb, Lu; its chemical constitution is Y:70%～90% by weight percentage, Er:5%～20%, Ho:1%～10%.
(2), by mass percentage be that 97%～91% AM60 magnesium alloy and mass percent are magnesium-Fu yttrium master alloy batching of 3%～9%, the AM60 magnesium alloy is preheating to 200 ℃, put into the heating of cast iron crucible, crucible is preheating to 300 ℃, and feeds SF
6: CO
2Volume ratio is 1: 200 a shielding gas; treat that magnesium alloy melts fully, add magnesium-Fu yttrium master alloy when melt temperature reaches 720 ℃; magnesium-Fu yttrium master alloy is preheating to 200 ℃; magnesium-Fu yttrium master alloy melts fully, and temperature rises to 740 ℃, and logical argon gas refining was stirred 10 minutes; left standstill then 30 minutes; when body temperature degree fusion drops to 700 ℃, on cold-chamber die casting machine, carry out die casting, obtain a kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains.
The beneficial effect that the present invention had is: the strength property of Mg-Al-Mn alloy is improved significantly, and its tensile strength, yield strength, unit elongation reach respectively: 235-250MPa, 110-117MPa, 7-10%.Under the same process condition, be significantly improved than the obdurability index (205MPa, 90MPa, 7%) of AM60 magnesium alloy, and the high advantage of this series magnesium alloy plasticity has also obtained enhancing.The corrosion resistance nature of Mg-Al-Mn alloy is greatly improved simultaneously, and the Mg-Al-Mn alloy corrosion speed of different content of rare earth is 0.35-0.77mg/cm
2Day obviously is better than the 6.9mg/cm of AM60 magnesium alloy
2Day.At last, compare with basic alloy A M60, alloy production process of the present invention does not have excessive variation, is convenient to promote the use of, and cost promotes and is not higher than 10%, and the extrusion process performance is good.
Compare with basic alloy A M60 magnesium alloy, characteristics of the present invention are:
1, the alloying that realizes adding rare earth element by thin brilliant effect, solid solution effect, the aging precipitation effect of adding the yttrium-rich RE generation effectively improves alloy mechanical property under the prerequisite of the excellent plasticity of this series magnesium alloy of not obvious change.2, the removal of impurities effect of yttrium-rich RE reduces impurity, gas, harmful trace metal equal size in the melt, thereby alloy corrosion resistance of the present invention is significantly improved, and practicality strengthens.3, replace common yttrium-rich RE with cheap special rich yttrium mixed rare earth and improve alloy property, high price element resources such as Eu, Dy, Tb, Lu had both been saved, the cost performance of magnesium alloy is obviously promoted, make the resources advantage of magnesium and rare earth obtain maximum performance.
Description of drawings
Fig. 1 is the sem photograph of the embodiment of the invention 2 alloys.
Fig. 2 is the embodiment of the invention 2 transmission electron microscope micro-organization charts.
The refined crystalline strengthening and the dispersion-strengthened action that as can be seen from the figure are the relative alloy generation of Al-RE of graininess disperse distribution are to make alloy mechanical property obtain the main cause that obviously improves.
Embodiment
Embodiment 1AM60+YErHo (Y=0.3%, Er=0.1%, Ho=0.1%) diecast magnesium alloy AM60+YErHo (Ho=0.1%) the diecast magnesium alloy preparation method is as follows for Y=0.3%, Er=0.1%:
1, preparation magnesium-Fu yttrium master alloy: by magnesium be 80%, rare earth is 20% relationship between quality proportion ingredient, magnesium ingot and mishmetal raw material are put into cast iron or plumbago crucible heat fused and are warming up to 780 ℃, are cast into magnesium-Fu yttrium intermediate alloy ingot after stirring.Feed SF in the fusion process
6: CO
2Volume ratio is 1: 200 a shielding gas.Preparing used special yttrium-rich RE is remaining cheap yttrium-rich RE behind common yttrium-rich RE extraction Eu, Dy, the high price elements such as Tb, Lu.
2, preparation high-strength antirusting Mg-Al-Mn die-casting magnesium alloy: by the AM60 magnesium alloy be 97.5%, magnesium-Fu yttrium master alloy is 2.5% relationship between quality batching, the AM60 alloy pig is preheating to 200 ℃, puts into the heating of cast iron crucible, crucible is preheating to 300 ℃, and feeds SF
6: CO
2Volume ratio is 1: 200 a shielding gas, treats that magnesium alloy melts fully, adds magnesium-Fu yttrium master alloy when melt temperature reaches 720 ℃, and magnesium-Fu yttrium master alloy is preheating to 200 ℃; When magnesium-Fu yttrium master alloy melts fully, when temperature rises to 740 ℃, lead to the argon gas refining and stirred 10 minutes, left standstill then 30 minutes, when body temperature degree fusion drops to 700 ℃, on cold-chamber die casting machine, carry out die casting, obtain containing the high-strength anti-corrosion die-casting magnesium alloy of yttrium-rich RE.
Obtained alloy is formed:
| Al | Mn | Y | Er | Ho | Fe | Cu | Si | Ni | Mg |
| 6.3 | 0.4 | 0.3 | 0.1 | 0.1 | ≤0.005 | ≤0.02 | ≤0.01 | ≤0.001 | Surplus |
By previous process steps preparation contain the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy, alloy property sees Table 1 and table 2.
Embodiment 2AM60+YErHo (Y=0.8%, Er=0.1%, Ho=0.05%) diecast magnesium alloy
(Ho=0.05%) diecast magnesium alloy is prepared burden by following mass percent for Y=0.8%, Er=0.1%: the AM60 magnesium alloy is 95% to AM60+YErHo, magnesium-Fu yttrium master alloy 5%.Its preparation method such as embodiment 1.
Obtained alloy is formed:
| Al | Mn | Y | Er | Ho | Fe | Cu | Si | Ni | Mg |
| 6 | 0.3 | 0.8 | 0.1 | 0.05 | ≤ 0.005 | ≤ 0.02 | ≤ 0.01 | ≤ 0.001 | Surplus |
By previous process steps preparation contain the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy, alloy property sees Table 1 and table 2.
Embodiment 3AM60+YErHo (Y=1.3%, Er=0.15%, Ho=0.1%) diecast magnesium alloy
(Ho=0.1%) by following mass percent batching: the AM60 magnesium alloy is 92% to AM60+YErHo, magnesium-Fu yttrium master alloy 8% for Y=1.3%, Er=0.15%.Its preparation method such as embodiment 1.
Obtained alloy is formed:
| Al | Mn | Y | Er | Ho | Fe | Cu | Si | Ni | Mg |
| 5.9 | 0.27 | 1.3 | 0.15 | 0.1 | ≤ 0.005 | ≤ 0.02 | ≤ 0.01 | ≤ 0.001 | Surplus |
By previous process steps preparation contain the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy, alloy property sees Table 1 and table 2.
Example 4AM60+YErHo (Y=1.5%, Er=0.1%, Ho=0.1%) diecast magnesium alloy
(Ho=0.1%) by following mass percent batching: the AM60 magnesium alloy is 91% to AM60+YErHo, magnesium-Fu yttrium master alloy 9% for Y=1.5%, Er=0.1%.Its preparation method such as embodiment 1.
Obtained alloy is formed:
| Al | Mn | Y | Er | Ho | Fe | Cu | Si | Ni | Mg |
| 5.8 | 0.27 | 1.5 | 0.1 | 0.1 | ≤ 0.005 | ≤ 0.02 | ≤ 0.01 | ≤ 0.001 | Surplus |
By previous process steps preparation contain the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy, alloy property sees Table 1 and table 2.
The room-temperature mechanical property comparison sheet of table 1 embodiment of the invention 1, example 2, example 3, example 4 and AM60
Table 1 is the result point out: the comprehensive mechanical property of alloy of the present invention promotes obviously: tensile strength improves 40MPa (20%), yield strength raising 20-27MPa (24%), unit elongation is promoted to 7-10%.The corrosion resistance nature comparison sheet of table 2 embodiment of the invention 1, example 2, example 3 and example 4 and AM60
Table 2 is the result point out: the erosion rate of alloy of the present invention has reduced 8-19 doubly than AM60 alloy, has improved the scope of practical application greatly.
Claims (2)
1. one kind contains the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy, it is characterized in that it is formed by mass percentage for Al is 5.7%～6.3%, Mn is 0.27%～0.4%, Y is 0.3%～1.5%, Er is 0.1%～0.15%, and Ho is 0.05%～0.1%, impurity element Fe≤0.02%, Cu≤0.002%, Si≤0.01%, Ni≤0.001%, surplus is a magnesium; This alloy is that 97%～9 1% AM60 magnesium alloy and mass percent are that magnesium-Fu yttrium master alloy of 3%～9% is made by mass percent; Described magnesium-Fu yttrium master alloy is to be that 80% magnesium and mass ratio are that 20% special yttrium-rich RE is made by mass ratio; Described special yttrium-rich RE is a remaining cheap yttrium-rich RE behind common yttrium-rich RE extraction Eu, Dy, the high price elements such as Tb, Lu, and special yttrium-rich RE chemical constitution is Y:70%～90% by mass percentage, Er:5%～20%, Ho:1%～10%.
2. require 1 described a kind of preparation method who contains the Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy as getting profit, it is characterized in that, step and condition are as follows: (1) is that 80% magnesium ingot and quality proportioning are that 20% rich yttrium mixed rare earth is a raw material by the quality proportioning, magnesium ingot and rich yttrium mixed rare earth raw material are put into cast iron or plumbago crucible heat fused and be warming up to 780 ℃, be cast into magnesium-Fu yttrium master alloy after stirring; Feed SF in the fusion process
6: CO
2Volume ratio is 1: 200 a shielding gas, described rich yttrium mixed rare earth is the yttrium-rich RE after common yttrium-rich RE extracts high price elements such as Eu, Dy, Tb, Lu, its chemical constitution is Y:70%～90% by weight percentage, Er:5%～20%, Ho:1%～10%;
(2) be that 97%～91% AM60 magnesium alloy and mass percent are magnesium-Fu yttrium master alloy batching of 3%～9% by mass percentage, the AM60 magnesium alloy is preheating to 200 ℃, put into the heating of cast iron crucible, crucible is preheating to 300 ℃, and feeds SF
6: CO
2Volume ratio is 1: 200 a shielding gas; treat that magnesium alloy melts fully, add magnesium-Fu yttrium master alloy when melt temperature reaches 720 ℃; magnesium-Fu yttrium master alloy is preheating to 200 ℃; magnesium-Fu yttrium master alloy melts fully, and temperature rises to 740 ℃, and logical argon gas refining was stirred 10 minutes; left standstill then 30 minutes; when body temperature degree fusion drops to 700 ℃, on cold-chamber die casting machine, carry out die casting, obtain a kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains.
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Effective date of registration: 20170228 Address after: Chinese magnesium Valley Park in Jilin province 134300 Baishan City Hunjiang District No. 1 Patentee after: Baishan City Tian An metal magnesium Mining Co., Ltd. Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |