CN101280379B - High-strength Mg-Zn-Ce-Ag alloy and preparation thereof - Google Patents
High-strength Mg-Zn-Ce-Ag alloy and preparation thereof Download PDFInfo
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- CN101280379B CN101280379B CN200710010867A CN200710010867A CN101280379B CN 101280379 B CN101280379 B CN 101280379B CN 200710010867 A CN200710010867 A CN 200710010867A CN 200710010867 A CN200710010867 A CN 200710010867A CN 101280379 B CN101280379 B CN 101280379B
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 76
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 230000006835 compression Effects 0.000 claims abstract description 18
- 238000007906 compression Methods 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 11
- 210000001787 dendrite Anatomy 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000013081 microcrystal Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 4
- 238000007712 rapid solidification Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- -1 magnesium rare earth Chemical class 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- HOWHQWFXSLOJEF-MGZLOUMQSA-N systemin Chemical compound NCCCC[C@H](N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(O)=O)C(=O)OC(=O)[C@@H]1CCCN1C(=O)[C@H]1N(C(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H]2N(CCC2)C(=O)[C@H]2N(CCC2)C(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](NC(=O)[C@H](C)N)C(C)C)CCC1 HOWHQWFXSLOJEF-MGZLOUMQSA-N 0.000 abstract 1
- 108010050014 systemin Proteins 0.000 abstract 1
- 238000007670 refining Methods 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
The invention relates to a magnesium alloy preparation technology, in particular to high strength Mg-Zn-Ce-Ag magnesium alloy and the preparation method thereof. The alloy belongs to the alloy systemin the magnesium rare earth system, and the components thereof are Mg, 1 percent of Zn, 2 percent of Ce and 1 percent of Ag (according to atom percentage ratio). The grain diameter of the primary crystal Alpha-Mg of the alloy is 10 to 40 micrometers, the grains of the second-phase Mg12Ce are distributed evenly and diffusedly, and the spacing of the secondary dendrites is 6 to 9 micrometers. The magnesium alloy of the invention is prepared through copper mold casting, the grains of the alloy are refined through the quick cooling of the copper mold casting technology, and the secondary phase isdistributed evenly and diffusedly, thus the magnesium alloy has high compression strength and plasticity. The invention develops a new method for preparing the Mg-Zn-Ce-Ag alloy with high compressionstrength, and thereby enlarges the application field of the magnesium alloy material.
Description
Technical field
The present invention relates to the magnesium alloy technology of preparing, be specially a kind of high-strength Mg-Zn-Ce-Ag alloy and preparation method thereof.
Background technology
Magnesium alloy has high specific tenacity and specific rigidity, the dimensional stability height, damping property, heat conductivility, castability and machinable are functional, be the lightest structural metallic materials of present industrial application and the functional materials of special purpose, magnesium alloy can be recycled, environmentally friendly, therefore be described as the green engineering structural metallic materials of 21 century again.
The development and application of magnesium alloy starts from the twenties in 20th century, and tempo is slow than steel and aluminium alloy, and its reason at first is that the oxide film of magnesium is not fine and close, and corrosion resistance nature is not as good as aluminium alloy.The crystalline structure of magnesium is a close-packed hexagonal, and plastic working is difficulty.Compare with aluminium alloy, Mg Alloy Research and development are also very insufficient, and Application of Magnesium is yet very limited.At present, the output of magnesium alloy has only 1% of aluminium alloy.Magnesium alloy is a foundry goods as the maximum purposes of structure applications, wherein is die casting more than 90%.Yet magnesium alloy is in balance or near equilibrated under the conventional curing condition, and microtexture and performance exist many shortcomings, thick as crystal grain and precipitated phase, element segregation is serious, thereby intensity, plasticity are lower, corrosion resistance nature is relatively poor etc., and this has limited the industrial applications of magnesium alloy.
In recent years, the various countries scholar furthers investigate magnesium alloy materials, particularly how improves and has done a large amount of work aspect the mechanical property.At present, the approach that improves magnesium alloy mechanical property mainly contains several different methods such as strain-hardening, grain refining, alloying, thermal treatment, magnesium alloy and ceramic phase be compound.
China has abundant magnesium resource, but because the magnesium alloy technology of preparing is grasped inadequately, many now with raw-material form outlet, lose bigger.Therefore research and develop magnesium alloy, the spy is that the magnesium alloy and the preparation technology thereof of high-strength high-plasticity is significant fully.
Summary of the invention
The object of the present invention is to provide a kind of high-strength Mg-Zn-Ce-Ag alloy and preparation method thereof, this method technology cost is low and simple and easy to do, and the magnesium alloy of acquisition has higher compression intensity and plasticity.
Technical scheme of the present invention is:
The invention provides a kind of high-strength Mg-Zn-Ce-Ag alloy, the magnesium alloy tissue is by the primary crystal α-Mg and second Mg mutually
12Ce forms, and wherein, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The shared volume fraction of Ce group is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12Ce phase particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m; Wherein, by atomic percent, matrix is primary crystal α-Mg, comprises 96-99%Mg, 0.6-2.5%Ce and 0-1.5%Ag, and Ce, Ag are present in the matrix with the form of solid solution; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 90.0-93.0%Mg, 4.0-6.0%Ce, 0.5-2.0%Ag and 2.0-4.0%Zn, and Zn, Ag are present in the second phase Mg with the form of solid solution
12Among the Ce).
High-strength Mg-Zn-Ce-Ag magnesium alloy of the present invention is strengthened the base reason: because rapid solidification makes the alloy grain refinement, refined crystalline strengthening has played main effect in this alloy, in addition, matrix interalloy element (Ce, Ag) be can not ignore and the solution strengthening effect and the second phase Mg caused
12Ce distributes uniformly and has caused the precipitation strength effect.
Prepared rapid solidification Mg-Zn-Ce-Ag alloy mechanical property index is as follows:
Compression yield strength σ
0.2=260-290MPa;
Compressed rupture strength σ
f=420-500MPa;
Compression plastic strain ε
p=6.5%-11%.
The described method for preparing high-strength Mg-Zn-Ce-Ag alloy, adopt copper mold to cast and prepare rapid solidification Mg-Zn-Ce-Ag alloy sample, magnesium alloy crystal grain obtains refinement, because grain refining and second precipitation strength of particle mutually make the intensity of Mg-Zn-Ce-Ag alloy be improved.The copper mold concrete processing parameter of casting is as follows: vacuum tightness 10
-1～10
-3Pa, 500～700 ℃ of temperature, speed of cooling 10～10
2K/s.
The advantage that the present invention has:
1, the present invention has adopted the Mg-Zn-Ce-Ag alloy, need not to improve the mechanical property of magnesium alloy by strain-hardening, increase rate of cooling but cast by copper mold, make crystal grain obtain refinement to obtain high-strength Mg-Zn-Ce-Ag alloy, the technology cost is low and simple and easy to do.
2, the present invention relates to magnesium alloy is magnesium rare earth-based alloy system, and its composition is Mg-1%Zn-2%Ce-1%Ag (atomic percent), adopts the method preparation of copper mold casting.The quick cooling of copper mold casting process makes the grain refining of alloy, second even mutually, the disperse distribution, thus make this magnesium alloy have high compressive strength and plasticity.The present invention has developed a kind of novel method for preparing high compression-strength Mg-Zn-Ce-Ag alloy, has expanded the Application Areas of magnesium alloy materials.
Description of drawings
Fig. 1 is the X-beta ray spectrum of copper mold cooling Mg-Zn-Ce-Ag alloy.
Fig. 2 is the optical photograph of copper mold cooling Mg-Zn-Ce-Ag alloy.
Fig. 3 is the stress under compression strain curve of copper mold cooling Mg-Zn-Ce-Ag alloy.
Embodiment
The present invention is described in detail in detail by the following examples.
Embodiment 1
The Mg-Zn-Ce-Ag alloying constituent comprises: 96%Mg, 1%Zn, 2%Ce, 1%Ag (atomic percent).
Mg-Zn-Ce-Ag alloy smelting method of the present invention is a routine techniques, and the present embodiment magnesium alloy adopts vacuum melting, and concrete processing parameter has: vacuum tightness 10
-1～10
-3Pa, 700～850 ℃ of Heating temperatures.With the alloy liquid that obtains in vacuum tightness 10
-2About 700 ℃ of Pa, temperature, casting by copper mold increases rate of cooling (rate of cooling 100K/s), makes crystal grain obtain refinement, to obtain high-strength Mg-Zn-Ce-Ag alloy.The magnesium alloy tissue is by the primary crystal α-Mg and second Mg mutually
12Ce forms, and in the present embodiment, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The shared volume fraction of Ce is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12The Ce particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m, the results are shown in Figure 2.Wherein, by atomic percent, matrix is primary crystal α-Mg, comprises 96.48-98.43%Mg, 0.95-2.08%Ce and 0.62-1.44%Ag, and Ce, Ag solid solution are in the Mg matrix; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 91.0-91.5%Mg, 4.0-4.9%Ce, 0.85-1.75%Ag and 2.25-3.25%Zn, and Zn, Ag are solid-solubilized in the second phase Mg
12Among the Ce.
Fig. 1 is the X-beta ray spectrum of copper mold cooling Mg-Zn-Ce-Ag alloy.Through X-ray diffraction analysis as can be known, this alloy comprises α-Mg, Mg among Fig. 1
12Ce phase two-phase.
Fig. 2 is the optical photograph of copper mold cooling Mg-Zn-Ce-Ag alloy.Fig. 2 has provided its typical tissue: the second phase Mg
12Ce quantity is more, and is linked to be network-like structure mostly, and is tiny chrysanthemum crystals form more.
Fig. 3 is the stress under compression and the strain curve of copper mold cooling Mg-Zn-Ce-Ag alloy.
Because grain refining and second precipitation strength of particle mutually make the intensity of Mg-Zn-Ce-Ag alloy be improved, this alloy has higher compressive strength, and its performance index are as follows: compression yield strength σ
0.2=285MPa; Compressed rupture strength σ
f=480MPa; Compression plastic strain ε
p=10.5%.
Relevant comparative example 1
The concrete processing parameter of Mg-Zn-Ce-Ag alloy smelting method is the same, and castingprocesses is to adopt liquid magnesium alloy, and teeming temperature is about 700 ℃, and ingate speed is 0.5m/s.
Performance index are as follows: compression yield strength σ
0.2=130MPa; Compressed rupture strength σ
f=275MPa; Compression plastic strain ε
p=8.5%.
Difference from Example 1 is:
With magnesium alloy liquid in vacuum tightness 10
-1About 700 ℃ of Pa, temperature, casting by copper mold increases rate of cooling (rate of cooling 50K/s), makes crystal grain obtain refinement, to obtain high-strength Mg-Zn-Ce-Ag alloy.In the present embodiment, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The mutually shared volume fraction of Ce is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12Ce phase particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m.Wherein, by atomic percent, matrix is primary crystal α-Mg, comprises 97.3-98.5%Mg, 1.0-2.3%Ce and 0.4-0.6%Ag, and Ce, Ag solid solution are in the Mg matrix; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 91.5-92%Mg, 4.5-5.0%Ce, 0.65-0.85%Ag and 2.4-3.0%Zn, and Zn, Ag are solid-solubilized in the second phase Mg
12Among the Ce.
Because grain refining and second precipitation strength of particle mutually improve the intensity of Mg-Zn-Ce-Ag alloy, this alloy has higher compressive strength, and its performance index are as follows: compression yield strength σ
0.2=265MPa; Compressed rupture strength σ
f=440MPa; Compression plastic strain ε
p=10.5%.
Embodiment 3
Difference from Example 1 is:
With magnesium alloy liquid in vacuum tightness 10
-3About 600 ℃ of Pa, temperature, casting by copper mold increases rate of cooling (rate of cooling 100K/s), makes crystal grain obtain refinement, to obtain high-strength Mg-Zn-Ce-Ag alloy.In the present embodiment, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The mutually shared volume fraction of Ce is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12Ce phase particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m.Wherein, by atomic percent, matrix is primary crystal α-Mg, comprises 97.5-98.5%Mg, 1.0-2.0%Ce and 0.45-0.6%Ag, and Ce, Ag solid solution are in the Mg matrix; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 91.5-92.5%Mg, 4.5-5.0%Ce, 0.70-0.85%Ag and 2.2-3.2%Zn, and Zn, Ag are solid-solubilized in the second phase Mg
12Among the Ce.
Because grain refining and second precipitation strength of particle mutually improve the intensity of Mg-Zn-Ce-Ag alloy, this alloy has higher compressive strength, and its performance index are as follows: compression yield strength σ
0.2=270MPa; Compressed rupture strength σ
f=470MPa; Compression plastic strain ε
p=9%.
Difference from Example 1 is:
With magnesium alloy liquid in vacuum tightness 10
-3About 500 ℃ of Pa, temperature, casting by copper mold increases rate of cooling (rate of cooling 30K/s), makes crystal grain obtain refinement, to obtain high-strength Mg-Zn-Ce-Ag alloy.In the present embodiment, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The mutually shared volume fraction of Ce is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12Ce phase particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m.Wherein, by atomic percent, matrix is primary crystal α-Mg, comprises 97.5-99.0%Mg and 1.0-2.5%Ce, and Ce, Ag solid solution are in the Mg matrix; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 90.5-92.0%Mg, 4.6-5.8%Ce, 0.58-0.89%Ag and 2.63-3.46%Zn, and Zn, Ag are solid-solubilized in the second phase Mg
12Among the Ce.
Because grain refining and second precipitation strength of particle mutually improve the intensity of Mg-Zn-Ce-Ag alloy, this alloy has higher compressive strength, and its performance index are as follows: compression yield strength σ
0.2=260MPa; Compressed rupture strength σ
f=425MPa; Compression plastic strain ε
p=7%.
Claims (3)
1. high-strength Mg-Zn-Ce-Ag alloy is characterized in that: the magnesium alloy tissue is by the primary crystal α-Mg and second Mg mutually
12Ce forms, and wherein, the shared volume fraction of primary crystal α-Mg is 40-60%, the second phase Mg
12The shared volume fraction of Ce is 40-60%, and the primary crystal α-Mg size of microcrystal of this alloy is 10-40 μ m, the second phase Mg
12The Ce particle is even, disperse distributes, and secondary dendrite arm spacing is 6-9 μ m;
By atomic percent, matrix is primary crystal α-Mg, comprises 96-99%Mg, 0.6-2.5%Ce and 0-1.5%Ag; The second phase Mg
12Ce is evenly distributed on the matrix, comprises 90.0-93.0%Mg, 4.0-6.0%Ce, 0.5-2.0%Ag and 2.0-4.0%Zn;
By atomic percent, described magnesium alloy composition is Mg-1%Zn-2%Ce-1%Ag.
2. according to the preparation method of the described high-strength Mg-Zn-Ce-Ag alloy of claim 1, it is characterized in that: adopt copper mold to cast and prepare rapid solidification Mg-Zn-Ce-Ag alloy sample, make magnesium alloy grains, the second phase particle precipitation is strengthened, and the intensity of Mg-Zn-Ce-Ag alloy is improved;
The copper mold concrete processing parameter of casting is as follows: vacuum tightness 10
-1～10
-3Pa, 500～700 ℃ of temperature, speed of cooling 10～10
2K/s.
3. according to the preparation method of the described high-strength Mg-Zn-Ce-Ag alloy of claim 2, it is characterized in that prepared magnesium alloy mechanical property index is as follows: compression yield strength σ
0.2=260-290MPa; Compressed rupture strength σ
f=420-500MPa; Compression plastic strain ε
p=6.5%-11%.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710010867A CN101280379B (en) | 2007-04-06 | 2007-04-06 | High-strength Mg-Zn-Ce-Ag alloy and preparation thereof |
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|---|---|
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| CN101280379B true CN101280379B (en) | 2010-05-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0166917B1 (en) * | 1984-06-07 | 1988-08-31 | Allied Corporation | High strength rapidly solidified magnesium base metal alloys |
| WO2006095999A1 (en) * | 2005-03-08 | 2006-09-14 | Dong-Hyun Bae | Mg alloys containing misch metal, manufacturing method of wrought mg alloys containing misch metal, and wrought mg alloys thereby |
-
2007
- 2007-04-06 CN CN200710010867A patent/CN101280379B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0166917B1 (en) * | 1984-06-07 | 1988-08-31 | Allied Corporation | High strength rapidly solidified magnesium base metal alloys |
| WO2006095999A1 (en) * | 2005-03-08 | 2006-09-14 | Dong-Hyun Bae | Mg alloys containing misch metal, manufacturing method of wrought mg alloys containing misch metal, and wrought mg alloys thereby |
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