CN101787472B - Heat-resistant forged magnesium-rare earth alloy and preparation method thereof - Google Patents
Heat-resistant forged magnesium-rare earth alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of metallurgy, and relates to a method for preparing a heat-resistant forged magnesium-rare earth alloy, which comprises the following steps: preheating to melt pure magnesium, adding an intermediate alloy and pure Zn in turn, heating, mixing and dissolving, adding a Mg-Zn alloy and stirring and mixing; performing electrorefining treatment on alloy melt, casting by adopting a continuous casting method, and pretreating a continuous casting; and finally, performing forging preheating treatment on the pretreated continuous casting, and forging the continuous casting into the heat-resistant forged magnesium-rare earth alloy. The magnesium alloy has mechanical properties such as room temperature strength, instantaneous high temperature strength and hardness superior to those of the traditional commercial AZ31, AZ60 forgeable magnesium alloys.
Description
Technical field
What the present invention relates to is rare earth alloy of a kind of metallurgical technology field and preparation method thereof, specifically is a kind of heat-resistant forged magnesium-rare earth alloy and preparation method thereof.
Background technology
Magnesium alloy is a lightest present structural metallic materials, has high specific tenacity and specific rigidity, and the epigeosphere magnesium resource is abundant.Owing under the dual-pressure of energy dilemma and environmental pollution, proposed lightweight requirements at space flight, aviation automobile and field of traffic such as electronic car, train, so the magnesium alloy potentiality that are widely used in above-mentioned field.
At present magnesium alloy is mainly by the moulding of die casting mode, but owing to bring defective such as pore in the press casting procedure easily in foundry goods, therefore the part for preparing often can not satisfy the application requiring of space flight and aviation, military industry field.Forging and pressing are a kind ofly not only can significantly improve alloy mechanical property, and have the production efficiency height, the precision advantages of higher of manufactured parts.But most of magnesium alloy of exploitation is because the relatively poor ability that has a strong impact on the magnesium alloy secondary deformation of plasticity ratio at present.At present AZ31, AZ60 are arranged developing the alloy designations that has that can be used in the magnesium alloy forging and pressing.These alloys have good room-temperature property, but since above-mentioned magnesium alloy contained-Mg
17Al
12Surpassing 200 ℃ in use temperature will decompose, and makes the rapid reduction of magnesium alloy strength of AZ series to have limited the application of AZ series magnesium alloy at the field of aerospace press forging greatly.Therefore the heat-stable forging and pressing magnesium alloy of development of new has great importance to enlarging the Application of Magnesium scope.Improve at present the magnesium alloy resistance to elevated temperatures mainly by adding rare earth element, studies show that rare earth element, especially Y, Nd etc., improving aspect magnesium alloy strength, thermotolerance, the resistance to corrosion effect remarkable, as WE54 and WE43 etc.
In recent years find heavy rare earth element such as Gd, Dy, Tb etc. in the research, in the intensity, particularly thermotolerance aspect that improve magnesium alloy, effect is better than other rare earth elements such as Y, Nd.Find through retrieval prior art, people such as P.H.Fu point out in Mater Sci EngA.2008486:183-192 (Materials science engineering): the rare earth Nd element is when passing through magnesium alloy strength, resistance toheat and corrosive nature, the magnesium alloy unit elongation is also improved, and unit elongation can reach 14% and 25% respectively under as cast condition and solid solution attitude room temperature.
In sum, present stage aerospace, military project and other industry in be badly in need of a kind of high strength, high heat resistance and erosion-resisting magnesium alloy with materials such as substitution of Al alloys.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of heat-resistant forged magnesium-rare earth alloy and preparation method thereof is provided, by adding alloying element (Nd, Ce, Zn, Zr) or changing the melting technology condition, obtain the directly magnesium-rare earth of forging molding of as cast condition, make this type of magnesium alloy have and to forge and press mechanical properties such as the superior room temperature strength of magnesium alloy, TRANSIENT HIGH TEMPERATURE intensity and hardness than traditional commerce AZ31, AZ60.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of heat-resistant forged magnesium-rare earth alloy, its component and mass percent are followed successively by: 0.5 ~ 3.6%Nd, 0.2 ~ 1.2%Zr, 0.1 ~ 1.2%Zn, 0 ~ 0.3%Ce, 0 ~ 1.5%Ca, to be less than 0.02% impurity element, surplus be Mg.
Described impurity element comprises: Si, Fe, Cu and Ni.
The present invention relates to the preparation method of above-mentioned heat-resistant forged magnesium-rare earth alloy, may further comprise the steps:
The first step, will add master alloy and pure Zn behind the pre-hot melt of pure magnesium successively, add the Mg-Zr alloy and mix, make the alloy liquation through the miscible back of heating.
Described preheating is melted processing and is meant: put into after pure magnesium is preheated to 180 ~ 220 ℃ and be connected with SF
6/ CO
2The melt in furnace of gas shield also is warming up to 710 ~ 730 ℃.
Described master alloy is meant: through Mg-Ca alloy, Mg-Nd alloy, the Mg-Ce alloy of 180 ~ 220 ℃ of preheatings;
Described pure Zn is meant: through the pure Zn of 180 ~ 220 ℃ of preheatings;
Described miscible being meant of heating: the pure magnesium that will be added with master alloy is warming up to 770 ~ 790 ℃;
Second goes on foot, the alloy liquation is carried out adopting continuous metal cast process to pour into a mould after electrorefining is handled, and then continuously cast bloom is carried out pre-treatment;
Described electrorefining is handled and is meant: with the alloy liquation be controlled in 770 ~ 790 ℃ down insulation be cooled to 745 ~ 755 ℃ after 20 ~ 40 minutes, electrorefining is warmed up to 770 ~ 790 ℃ and left standstill 20 ~ 40 minutes after 6 ~ 10 minutes;
Described continuous metal cast process is meant: with the pouring speed of 20 ~ 200mm/min control teeming temperature is 680 ~ 740 ℃, the secondary cooling water flow control every millimeter of crystallizer girth at 1500 ~ 4500mm
3Pour into a mould under the environment of/min.
Described pre-treatment is meant any one in the following dual mode:
A) the control homogenization temperature is 380 ~ 420 ℃, and homogenization time is 0 ~ 8 hour;
B) adopt solution treatment, the control solid solubility temperature is 480 ~ 520 ℃, and the solution treatment time is 4 ~ 12 hours.
The 3rd step, forge and press after pretreated continuously cast bloom forged and pressed thermal pretreatment, make heat-resistant forged magnesium-rare earth alloy.
Described forging and pressing thermal pretreatment is meant: continuously cast bloom was placed under 400 ~ 500 ℃ the temperature preheating 0.5 ~ 4 hour;
The strain rate of described forging and pressing is 0.001 ~ 10S
-1
Compared with prior art, the present invention adopts the Mg-Nd master alloy to add the Nd element indirectly, can effectively more low-alloyed smelting temperature, reduce the utilization ratio of bringing more inclusion and improving rare earth in the fusion process; During with the Zr crystal grain thinning, thereby can the refinement alloy grain can effectively reduce the microsegregation of the inner solute of alloy; Can effectively improve the flame retardant properties of this alloy by adding a spot of Ca, thereby effectively stop the burning possibility of alloy in casting process, the final purpose that reduces the alloy inner inclusion and simplify continuous casting process that arrives.Can weaken texture in the magnesium alloy deformation process by adding a small amount of Ce, thereby the deformability that improves this alloy is to reach the forgeable purpose of as cast condition, since this magnesium-rare earth can be under as cast condition direct forging forming, reduced the preceding pretreated link of alloy of forging and pressing, therefore can reduce the cost of magnesium alloy forging forming greatly, alloy by the continuous cast method preparation can effectively reduce defectives such as inner shrinkage porosite of alloy and shrinkage cavity, thereby effectively improve the utilization ratio of Mg-Nd-Ce-Zn-Ca-Zr alloy billet, utilize the more common commercial malleable AZ60 of Mg-Nd-Ce-Zn-Ca-Zr alloy of this method preparation, the mechanical property and the resistance toheat of AZ31 magnesium alloy all obviously improve, and both prices are similar.Thereby can effectively enlarge the Application of Magnesium scope.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The melting technology of Mg-Nd-Ce-Zn-Ca-Zr alloy is: (1) prepares alloy according to alloying constituent, earlier pure magnesium, Mg-Nd, Mg-Ce, Mg-Ca, Mg-Zr master alloy is preheating to 200 ℃, pure magnesium is put into be connected with SF then
6/ CO
2The melt in furnace of gas shield.(2) treat that the magnesium liquid temp is raised to 720 ℃ after, in the magnesium melt, add Mg-Ca, Mg-Nd, Mg-Ce master alloy and pure Zn, after the above-mentioned master alloy fusing magnesium liquid temp is raised to the Mg-Zr master alloy that adds again after 780 ℃, treats to skim surface scum after its fusing, stirred 2 ~ 3 minutes.(3) the magnesium liquid temp is risen to 780 ℃ of insulations again and be cooled to 750 ℃ after 30 minutes, constantly electrorefining is 6 ~ 10 minutes, is warmed up to 780 ℃ after the refining and leaves standstill 30 minutes.(4) in order to reduce inner shrinkage porosite of ingot casting and shrinkage cavity, adopt the continuous casting method.The processing parameter of continuous casting is: casting speed is at 20 ~ 200mm/min, 680 ~ 740 ℃ of teeming temperatures, the secondary cooling water flow control every millimeter of crystallizer girth at 1500 ~ 4500mm
3/ min.
The Mg-Nd-Ce-Zn-Ca-Zr alloy 450 ℃ of following preheatings 2 hours, forge and press afterwards.The strain rate of forging and pressing is 1S
-1, then the forging and pressing alloy was carried out 200 ℃ of following artificial agings 2 hours, obtain high-strength temperature-resistant forging and pressing Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy at last.
The as cast condition directly room-temperature mechanical property of forging forming Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy continuous casting attitude is:
Tensile strength: 195MPa, yield strength: 118MPa, unit elongation: 16.5%.
High-strength temperature-resistant forging and pressing magnesium alloy forging and pressing attitude mechanical property is:
Tensile strength: 279MPa, yield strength: 269MPa, unit elongation: 12%.
The mechanical property of high-strength temperature-resistant forging and pressing Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy T5 attitude is:
Tensile strength: 324MPa, yield strength: 318MPa, unit elongation: 11%.
Embodiment 2
The melting technology of Mg-Nd-Ce-Zn-Ca-Zr alloy is: (1) prepares alloy according to alloying constituent, earlier pure magnesium, Mg-Nd, Mg-Ce, Mg-Ca, Mg-Zr master alloy is preheating to 200 ℃, pure magnesium is put into be connected with SF then
6/ CO
2The melt in furnace of gas shield.(2) treat that the magnesium liquid temp is raised to 720 ℃ after, in the magnesium melt, add Mg-Ca, Mg-Ce, Mg-Nd master alloy and pure Zn, after the above-mentioned master alloy fusing magnesium liquid temp is raised to the Mg-Zr master alloy that adds again after 780 ℃, treats to skim surface scum after its fusing, stirred 2 ~ 3 minutes.(3) the magnesium liquid temp is risen to 780 ℃ of insulations again and be cooled to 750 ℃ after 30 minutes, constantly electrorefining is 6 ~ 10 minutes, is warmed up to 780 ℃ after the refining and leaves standstill 30 minutes.(4) in order to reduce inner shrinkage porosite of ingot casting and shrinkage cavity, adopt the continuous casting method.The processing parameter of continuous casting is: casting speed is at 20 ~ 200mm/min, 680 ~ 740 ℃ of teeming temperatures, the secondary cooling water flow control every millimeter of crystallizer girth at 1500 ~ 4500mm
3/ min.
The solid solution temperature of Mg-Nd-Ce-Zn-Ca-Zr alloy is 520 ℃, and solution time is 4 hours, afterwards forging and pressing in 2 hours 450 ℃ of following preheatings the Mg-Nd-Ce-Zn-Ca-Zr alloy.The strain rate of forging and pressing is 1S
-1, then the forging and pressing alloy was carried out 200 ℃ of following artificial agings 4 hours, obtain high-strength temperature-resistant forging and pressing Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy at last.
The as cast condition directly room-temperature mechanical property of forging molding Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy continuous casting attitude is:
Tensile strength: 195MPa, yield strength: 118MPa, unit elongation: 16.5%.
High-strength temperature-resistant forging and pressing magnesium alloy forging and pressing attitude mechanical property is:
Tensile strength: 260MPa, yield strength: 245MPa, unit elongation: 12%.
The mechanical property of high-strength temperature-resistant forging and pressing Mg-Nd-Ce-Zn-Ca-Zr magnesium alloy T5 attitude is:
Tensile strength: 335MPa, yield strength: 324MPa, unit elongation: 11%.
Claims (1)
1. the preparation method of a heat-resistant forged magnesium-rare earth alloy, the component and the mass percent of this heat-resistant forged magnesium-rare earth alloy are followed successively by: 0.5～3.6%Nd, 0.2～1.2%Zr, 0.1～1.2%Zn, 0～0.3%Ce, 0～1.5%Ca, to be less than 0.02% impurity element, surplus be Mg; Described impurity element comprises: Si, Fe, Cu and Ni, it is characterized in that, and said method comprising the steps of:
The first step, will add master alloy and pure Zn behind the pre-hot melt of pure magnesium successively, add the Mg-Zr alloy and mix, make the alloy liquation through the miscible back of heating;
Second goes on foot, the alloy liquation is carried out adopting continuous metal cast process to pour into a mould after electrorefining is handled, and then continuously cast bloom is carried out pre-treatment;
The 3rd step, forge and press after pretreated continuously cast bloom forged and pressed thermal pretreatment, make heat-resistant forged magnesium-rare earth alloy;
Described preheating is melted processing and is meant: put into after pure magnesium is preheated to 180～220 ℃ and be connected with SF
6/ CO
2The melt in furnace of gas shield also is warming up to 710～730 ℃;
Described master alloy is meant: through Mg-Ca alloy, Mg-Nd alloy, the Mg-Ce alloy of 180～220 ℃ of preheatings;
Described miscible being meant of heating: the pure magnesium that will be added with master alloy is warming up to 770～790 ℃;
Described electrorefining is handled and is meant: with the alloy liquation be controlled in 770～790 ℃ down insulation be cooled to 745～755 ℃ after 20～40 minutes, electrorefining is warmed up to 770～790 ℃ and left standstill 20～40 minutes after 6～10 minutes;
Described continuous metal cast process is meant: with the pouring speed of 20～200mm/min, the control teeming temperature is 680～740 ℃, the secondary cooling water flow control every millimeter of crystallizer girth at 1500～4500mm
3Pour into a mould under the environment of/min;
Described pre-treatment is meant any one in the following dual mode:
A) the control homogenization temperature is 380～420 ℃, and homogenization time is 0～8 hour;
B) adopt solution treatment, the control solid solubility temperature is 480～520 ℃, and the solution treatment time is 4～12 hours;
Described forging and pressing thermal pretreatment is meant: continuously cast bloom was placed under 400～500 ℃ the temperature preheating 0.5～4 hour;
The strain rate of described forging and pressing is 0.001～10S
-1
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| EP2481825B1 (en) * | 2011-02-01 | 2013-05-08 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium alloy containing rare earth metals |
| EP2848333B1 (en) | 2013-09-16 | 2021-03-24 | Mubea Carbo Tech GmbH | Method and device for producing a metallic component by means of a casting and mould |
| CN104099507A (en) * | 2014-07-14 | 2014-10-15 | 沈阳工业大学 | High-strength and high-toughness rare earth magnesium alloy |
| CN104498796A (en) * | 2014-12-15 | 2015-04-08 | 苏州昊卓新材料有限公司 | Preparation method of Mg alloy |
| CN104946948A (en) * | 2015-06-16 | 2015-09-30 | 上海交通大学 | High-elasticity-modulus cast magnesium alloy and preparation method thereof |
| CN104928546B (en) * | 2015-06-16 | 2017-11-14 | 上海交通大学 | A kind of high strength and modulus casting magnesium-rare earth alloy and preparation method thereof |
| CN105463282A (en) * | 2015-12-03 | 2016-04-06 | 嘉瑞科技（惠州）有限公司 | Rare earth-magnesium alloy and preparation method thereof |
| CN105908040B (en) * | 2016-06-22 | 2017-12-05 | 南昌航空大学 | A kind of preparation method of semi-solid-state shaping Mg Gd Zn Ni Zr magnesium-rare earths and its semi-solid blank |
| CN106367649A (en) * | 2016-09-30 | 2017-02-01 | 肖旅 | Magnesium alloy easy to prepare and plastically form and component manufacturing method thereof |
| CN106435316A (en) * | 2016-11-01 | 2017-02-22 | 上海航天精密机械研究所 | Flame-resistant Mg-Nd magnesium alloy and casting method for sand casting thereof |
| CN108425052A (en) * | 2018-04-13 | 2018-08-21 | 上海海洋大学 | A kind of heat-resistance high-strength wrought magnesium alloy and preparation method thereof |
| CN109295369A (en) * | 2018-11-23 | 2019-02-01 | 上海交通大学 | One kind magnesium alloy containing cerium mischmetal and its heat treatment method |
| CN114351020B (en) * | 2021-12-30 | 2022-12-13 | 台山市中镁科技有限公司 | Magnesium alloy casting and preparation method and application thereof |
| CN115852224A (en) * | 2022-12-30 | 2023-03-28 | 上海交通大学 | Corrosion-resistant magnesium alloy and preparation method thereof |
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| US4116731A (en) * | 1976-08-30 | 1978-09-26 | Nina Mikhailovna Tikhova | Heat treated and aged magnesium-base alloy |
| IL147561A (en) * | 2002-01-10 | 2005-03-20 | Dead Sea Magnesium Ltd | High temperature resistant magnesium alloys |
| AUPS311202A0 (en) * | 2002-06-21 | 2002-07-18 | Cast Centre Pty Ltd | Creep resistant magnesium alloy |
| CN100513606C (en) * | 2007-09-06 | 2009-07-15 | 北京有色金属研究总院 | Heat conductive magnesium alloy and method for preparing the same |
| WO2009039581A1 (en) * | 2007-09-28 | 2009-04-02 | Cast Crc Limited | Permanent mould cast magnesium alloy |
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