CN101824572B - High-intensity and anti-corrosion Mg-Al-Zn-RE extruded magnesium alloy rich in Y-base rare earth alloy as well as production method and application thereof - Google Patents
High-intensity and anti-corrosion Mg-Al-Zn-RE extruded magnesium alloy rich in Y-base rare earth alloy as well as production method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-intensity and anti-corrosion Mg-Al-Zn-RE extruded magnesium alloy rich in Y-base rare earth alloy as well as a production method and application thereof, belonging to the field of light metal materials. The preparation method comprises the following steps of: adding Mg-Y rich intermediate alloy in the AZ31 melting process under the protection of gases of SF6 and CO2; introducing argon when the temperature of a melt is 720-740 DEG C, refining and stirring; standing, and then casting to form a high-intensity and anti-corrosion magnesium alloy material rich in Y; heating to 340-360 DEG C, keeping the temperature for 3-5h, extruding and producing on a horizontal extruder, wherein the temperature of a mould is 400-420 DEG C and the extruding speed is 1.2-1.6m/min; and stretching and straightening to obtain a high-intensity and anti-corrosion magnesium alloy thermal extruded section containing rare earth alloy rich in Y. The invention needs no special fire protection process in the deformation process and has less material consumption, high precision, small thickness and light weight.
Description
Technical field
The present invention relates to belong to light metal material class field, particularly have the extrusion forming process of the Mg-Al-Zn-RE magnesium alloy of high strength anti-corrosion.
Background technology
Magnesium is with its light weight, than stiffness height, specific tenacity height, damping anti-noise, anti-electromagnetic-radiation be easy to reclaim (not producing pollution) and the favor that is subjected to metallic substance, especially because magnesium alloy adapts to the world trends megatrend that production requires lightweight, environmental protection and energy saving, magnesium resource is abundant especially, be fit to STRATEGIES OF SUSTAINABLE DEVELOPMENT demand (and conventional metals resources such as iron, aluminium are exhausted day by day), thereby magnesium alloy becomes the research and development focus of countries in the world.Intensity is hanged down and solidity to corrosion is not high, close-packed hexagonal lattice crystal modification drag is big yet traditional magnesium alloy such as magnalium zinc alloy (AZ31) extrusion magnesium alloy exist, be difficult for extrusion molding, weakness such as corrosion resisting property difference, and can not satisfy the requirement of military project and vehicles power system.In addition, it is inflammable that magnesium alloy has oxidation, and there is the shortcoming than wildfire hidden danger in the processing and manufacturing process.
Alloying is to promote the most effective a kind of method of magnesium alloy strength, and rare earth (especially yttrium) is the element of the most practical of magnesium alloy chemical and tool development and application values.Because yttrium is identical with the crystalline structure of magnesium metal, belong to hexagonal close packed lattice together, the atomic radius of the two, lattice parameter are approaching, crystallization nucleation core principles according to " dimensional structure is complementary ", yttrium can be used as the heterogeneous forming core core of magnesium alloy, hinder grain growth, thereby magnesium alloy is produced significant thinning effect.In addition, the activity of yttrium is stronger, and impurity elements such as sulphur, oxygen are had stronger avidity, produces the cleaning action of degasification removal of impurities.Other elements such as aluminium, zinc etc. can produce alloying action in yttrium and magnesium and the magnesium alloy, produce solution strengthening, aging precipitation effect, form the second phase material of high-melting-point high thermal stability, produce dispersion-strengthened action.Yttrium had both promoted the intensity of alloy to these effects that magnesium alloy produces, and had increased corrosion resistance of alloy again, was generally acknowledged by Chinese scholars.But the problem of existence is: pure yttrium is somewhat expensive, and secondly the cost height is to have the part rare earth element to producing the magnesium yittrium alloy disadvantageous effect to be arranged.
Summary of the invention
The present invention's first purpose is the intensity that exists at present AZ31 extrusion magnesium alloy and solidity to corrosion is not high, close-packed hexagonal lattice crystal modification drag big, be difficult for the weakness of extrusion molding, and magnesium alloy to have an oxidation inflammable, there is the shortcoming than wildfire hidden danger in the processing and manufacturing process, proposes a kind of anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength that contains.
The chemical constitution of magnesium alloy of the present invention is respectively Al:2.5%～3.2% by weight percentage, Zn:0.6～1.2%; Rare earth is Y:0.1%～1.5%, Er:0.01%～0.15%, Ho:0.01%～0.1%, Gd:0.01%～0.2%; Impurity element is Fe≤0.02%, Cu≤0.002%, and Si≤0.01%, Ni≤0.001%, surplus is a magnesium.
Rich yttrium mixed rare earth also contains heavy rare earth element such as rare expensive Tb, Dy, Tu, Lu and produces disadvantageous Sm, Eu and Yb valence variation element to making rich yttrium-magnesium alloy usually except that containing yttrium (Y).The present invention has removed rare expensive Tb, Dy, heavy rare earth element and disadvantageous Sm, Eu and Yb valence variation elements such as Tu, Lu wherein, Ho, Er and the Gd rare earth element that will help the magnesium alloy performance are stayed in the yttrium-rich RE, to bring into play these rare earths and yttrium to promoting the combined effect of magnesium alloy performance, not only promote quality product, also greatly reduce the cost of raw material.Adopt magnesium alloy ingot of the present invention to carry out extrusion molding and produce metallic substance, have intensity height, solidity to corrosion height, close-packed hexagonal lattice crystal modification drag is little, extensibility is high, extrusion molding and production process do not have the advantage of disaster hidden-trouble easily.
Another object of the present invention is that above magnesium alloy is proposed a kind of feasible extrusion production technology:
At SF
6And CO
2Gas shield under; after treating AZ31 alloy substrate material melts; add and be preheating to magnesium-Fu yttrium master alloy of 200～220 ℃; feeding the argon gas refining when melt temperature is 720 ℃～740 ℃ stirred 10～15 minutes; left standstill then 30～40 minutes; when body temperature degree fusion is 690 ℃～710 ℃, is cast as and contains rich yttrium high-strength magnesium alloy ingot casting.
The present invention adds cheap practical rich yttrium mixed rare earth on original AZ31 alloy basis, not only technology is simple, is easy to production control, and the magnesium alloy quality stability that forms is good.
SF of the present invention
6And CO
2Volume ratio be 1: 100.
The extruding that the 3rd purpose of the present invention provides the Mg-Al-Zn-RE distortion shape magnesium alloy that contains rich yttrium produces, uses, and the described yttrium-rich RE wrought magnesium alloys that contains is used for the extrusion production section bar.
Concrete method is: described magnesium alloy ingot is heated to 340 ℃～360 ℃ through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.2 meters/minute～1.8 meters/minute, and the drawn alignment handles, and obtains containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE.
Extrusion process of the present invention need not to carry out anti-especially ignition technique, owing to contain the high strength anti-corrosion magnesium alloy unit elongation height of rich yttrium, is easy to be shaped few, the thin thickness, in light weight of the shape materials of shaping.
Embodiment
One, selecting for use of magnesium-Fu yttrium master alloy:
Select magnesium-Fu yttrium master alloy for use, the weight percent of each composition is Y:20%～90%, Er:5%～20%, Ho:5%～10%, Gd:10%～30% in magnesium-Fu yttrium master alloy by analysis.
Two, contain the Mg-Al-Zn-RE wrought magnesium alloys preparation of rich yttrium:
The AZ31 matrix alloy of Mg, Al, Zn preparation is preheating to 220 ℃, puts into (crucible is preheating to 300 ℃) in the crucible, and feed SF
6: CO
2Volume ratio is 1: 100 a shielding gas; after treating that basic alloy melts fully; when reaching 720 ℃～740 ℃, melt temperature adds magnesium-Fu yttrium master alloy (being preheating to 200～220 ℃ earlier); feed shielding gas then while stirring; melt fully up to the magnesium-Fu yttrium master alloy that adds; logical argon gas refining was stirred 10～15 minutes when temperature controls to 720 ℃～740 ℃; left standstill then 30～40 minutes; cast when treating 690 ℃～710 ℃ of melts, be prepared into and contain rich yttrium high strength anti-corrosion magnesium alloy materials.
The extrusion magnesium alloy middle-weight rare earths content of preparation is Y:0.1%～1.5%, Er:0.01%～0.15%, Ho:0.01%～0.1%, Gd:0.01%～0.2%.
Three, contain rich yttrium high strength anti-corrosion Mg-Al-Zn-RE wrought magnesium alloys extrusion production, application
Contain rich yttrium high strength anti-corrosion Mg-Al-Zn-RE wrought magnesium alloys and be heated to 340 ℃～360 ℃ described through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.2 meters/minute～1.8 meters/minute, and, obtain containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE through 180 ℃ of insulations artificial aging processing in 16 hours.
Example 1:AZ31+ rich Y (Er, Ho, Gd) (Y=0.1%, Er=0.15%, Ho=0.1%, Gd=0.2%) alloy contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength, and its weight percent proportioning is: aluminium: 2.5%, and zinc: 1.0%, Y:0.1%, Er:0.15%, Ho:0.1%, Gd:0.2%, impurity element Fe≤0.02%, Cu≤0.002%, Si≤0.01%, Ni≤0.001%, surplus are magnesium.Described magnesium alloy ingot is heated to 340 ℃～360 ℃ through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.4 meters/minute～1.8 meters/minute, and the drawn alignment handles, and obtains containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE.Alloy property sees Table 1 and table 2.
(Ho=0.05%) alloy contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength to the rich Y (Er, Ho) of example 2:AZ31+ for Y=0.9%, Er=0.1%, its weight percent proportioning is: aluminium: 3.0%, zinc: 1.2%, Y:0.9%, Er:0.1%, Ho:0.05%, impurity element Fe≤0.02%, Cu≤0.002%, Si≤0.01%, Ni≤0.001%, surplus are magnesium.Described magnesium alloy ingot is heated to 340 ℃～360 ℃ through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.2 meters/minute～1.5 meters/minute, and the drawn alignment handles, and obtains containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE.Alloy property sees Table 1 and table 2.
Embodiment 3:AZ31+ rich Y (Er, Ho, Gd) (Y=1.5%, Er=0.12%, Ho=0.08%, Gd=0.1%) alloy contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength, and its weight percent proportioning is: aluminium: 3.2%, and zinc: 0.6%, Y:1.5%, Er:0.12%, Ho:0.08%, Gd:0.1%, impurity element Fe≤0.02%, Cu≤0.002%, Si≤0.01%, Ni≤0.001%, surplus are magnesium.Described magnesium alloy ingot is heated to 340 ℃～360 ℃ through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.2 meters/minute～1.4 meters/minute, and the drawn alignment handles, and obtains containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE.Alloy property sees Table 1 and table 2
The room-temperature mechanical property of table 1 embodiment of the invention 1,2,3 and the deck watch of AZ31
| Alloy | Draw intensity (MPa) | Yield strength (MPa) | Unit elongation (%) |
| AZ31 | 230 | 195 | 8 |
| Embodiment 1 | 280 | 240 | 11 |
| Embodiment 2 | 292 | 251 | 12 |
| Embodiment 3 | 286 | 235 | 10 |
The corrosion resistance nature of table 2 embodiment of the invention 1,2,3 and the deck watch of AZ31
| Alloying constituent | Corrosion speed (mg/cm 2day) |
| AZ31 | 4.50 |
| Embodiment 1 | 1.05 |
| Embodiment 2 | 1.12 |
| Embodiment 3 | 0.98 |
As seen from the above table, the present invention has pull resistance, erosion resistance and better extensibility preferably than AZ31.
Characteristics of the present invention:
1, novel yttrium-rich RE is in the magnesium alloy smelting process, remove impurity, receive the cleaning action of degasification (such as H2), slagging-off (MgO), removal of impurities (as Fe, Cu, Ni) etc., eliminate or reduce their damaging effect, thereby promote its intensity, corrosion resisting property and extrusion processing performance.
2, novel yttrium-rich RE is that the present invention is in order to promote effective alloying element of its improved strength extrusion performance, its mechanism is: one, add the remarkable alloy structure of rare earth, the yttrium-rich RE enrichment is because of forward position, liquid interface in process of setting, the formation composition is crossed cold resistance and is hindered grain growth, effective refinement alloy structure, crystal grain diminishes many, has both improved the extrusion processing performance, has improved the anti-fracture energy of alloy substrate again.Two, the dispersion-strengthened of rare earth phase alloy, the adding of yttrium-rich RE (comprising elements such as yttrium, holmium, erbium, gadolinium) generates tiny and rare earth intermetallic compound particulate that disperse distributes, and originally the fragility of continuous distribution becomes broken mutually, help pinning crystal boundary and dislocation, thereby improve intensity.
3, behind the interpolation rare earth element, generate tiny and disperse rare earth intermetallic compound Particle Distribution are at the crystal boundary place of magnesium alloy, particulate produces slippage during hot extrusion, reduced drag widely, simultaneously, because the activity of yttrium is stronger, contained the formation of Mg O in the alloy effectively, be more conducive to extrusion molding, make that the hot extrusion technique of magnesium alloy is more reliable and stable.In addition, behind the adding yttrium-rich RE, the combustion initiation temperature of alloy has improved 70 ℃, has reduced the disaster hidden-trouble in the course of processing, has effectively guaranteed the security of magnesium alloy process of manufacture.
4, to adopt novel yttrium-rich RE be additive in the present invention, the magnesium-rare earth of being researched and developed, benefit is: the one, reduced the cost of alloy, contain the rich yttrium mixed rare earths of high price such as Tb, Dy, Tu, Lu with novel rich yttrium mixed rare earth replacement cheaply, can make the rare earths material cost reduce by 50%, save resources such as Tb in short supply, Dy, Tu, Lu simultaneously.The 2nd, for separation remove Sm, Eu, Dy, Tb, Tu, Lu after remaining a large amount of novel rich yttriums that overstock found a new application approach, help alleviating the unbalanced contradiction of rare earth resources production and marketing, promote the rare earth resources high-efficiency comprehensive utilization.
Claims (4)
1. contain the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength, it is characterized in that the chemical constitution of described magnesium alloy is respectively Al:2.5%～3.2% by weight percentage, Zn:0.6～1.2%; Yttrium-rich RE is Y:0.1%～1.5%, Er:0.01%～0.15%, Ho:0.01%～0.1%, Gd:0.01%～0.2%; Impurity element is Fe≤0.02%, Cu≤0.002%, and Si≤0.01%, Ni≤0.001%, surplus is a magnesium.
2. a production method that contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength according to claim 1 is characterized in that at SF
6And CO
2Gas shield under, after treating AZ31 alloy substrate material melts, add and be preheating to magnesium-Fu yttrium master alloy of 200～220 ℃, feeding the argon gas refining when melt temperature is 720 ℃～740 ℃ stirred 10～15 minutes, left standstill then 30～40 minutes, when body temperature degree fusion is 690 ℃～710 ℃, is cast as and contains rich yttrium high-strength magnesium alloy ingot casting; The weight percent of each composition is Y:20%～90%, Er:5%～20%, Ho:5%～10%, Gd:10%～30% in described magnesium-Fu yttrium master alloy, and surplus is a magnesium, and the weight total amount of each composition is 100% in described magnesium-Fu yttrium master alloy.
3. application that contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength according to claim 1 is characterized in that containing rich yttrium high strength anti-corrosion magnesium alloy ingot and being used for the extrusion production section bar described.
4. according to the described application that contains the anti-corrosion Mg-Al-Zn-RE extrusion magnesium alloy of Yttrium-rich rare earth high-strength of claim 3, it is characterized in that described magnesium alloy ingot is heated to 340 ℃～360 ℃ through resistance furnace, be incubated 3～5 hours, on horizontal extruder, carry out extrusion production, 400～420 ℃ of die temperatures, extrusion speed is 1.2 meters/minute～1.8 meters/minute, and drawn alignment processing, obtains containing the high strength anti-corrosion magnesium alloy hot extruded shapes of yttrium-rich RE.
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| CN102864551A (en) * | 2012-07-13 | 2013-01-09 | 鹤壁银龙有色金属科技有限公司 | Preparation method of magnesium alloy heald frame of air-jet loom |
| CN107177762A (en) * | 2017-05-18 | 2017-09-19 | 湖南金戈新材料有限责任公司 | The secondary hot extrusion technique of AQ80M magnesium alloy profiles |
| CN109082582B (en) * | 2018-09-10 | 2019-08-09 | 东北大学 | A kind of the magnesium-based high-entropy alloy and preparation method of high-strength tenacity high rigidity |
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| CN1789457A (en) * | 2004-12-17 | 2006-06-21 | 长沙市美克科技开发有限公司 | Thin-grain high-plasticity rare earth-containing wrought magnesium alloys |
| CN101469387A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院长春应用化学研究所 | Yttrium-rich rare earth high-strength heat-resistant creep-resistant die-casting magnesium alloy |
| CN100554466C (en) * | 2008-05-21 | 2009-10-28 | 中国科学院长春应用化学研究所 | A kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains |
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| JP3107267B2 (en) * | 1992-12-04 | 2000-11-06 | トヨタ自動車株式会社 | Heat resistant magnesium alloy |
| CN101228286A (en) * | 2005-05-26 | 2008-07-23 | 铸造中心有限公司 | Hpdc magnesium alloy |
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| CN1789457A (en) * | 2004-12-17 | 2006-06-21 | 长沙市美克科技开发有限公司 | Thin-grain high-plasticity rare earth-containing wrought magnesium alloys |
| CN101469387A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院长春应用化学研究所 | Yttrium-rich rare earth high-strength heat-resistant creep-resistant die-casting magnesium alloy |
| CN100554466C (en) * | 2008-05-21 | 2009-10-28 | 中国科学院长春应用化学研究所 | A kind of Yttrium-rich rare earth high-strength antirusting Mg-Al-Mn die-casting magnesium alloy that contains |
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