CN101463442A - Casting magnesium alloy containing Ag and heavy rare earth and preparation thereof - Google Patents
Casting magnesium alloy containing Ag and heavy rare earth and preparation thereof Download PDFInfo
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- CN101463442A CN101463442A CNA2009100454094A CN200910045409A CN101463442A CN 101463442 A CN101463442 A CN 101463442A CN A2009100454094 A CNA2009100454094 A CN A2009100454094A CN 200910045409 A CN200910045409 A CN 200910045409A CN 101463442 A CN101463442 A CN 101463442A
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Abstract
The invention relates to a casting magnesium alloy containing Ag and heavy rare earth of the technical field of metallic materials and a preparation method thereof. The magnesium alloy comprises the following components according to the mass percent: 6-10% of GD, 0.5-4% of Y, 0.2-3% of Ag, 0.35-0.7% of Zr, less than 0.02% of impurity elements of Fe, Cu, Ni and the rest is Mg. The magnesium alloy is obtained by smelting and the subsequent heat treatment. The invention has simple technique, high production efficiency. The magnesium alloy contains lower rare-earth, has very excellent room temperature strength and plasticity. The combination with different high performances can be obtained by adjusting alloying components and the technology for heating processing.
Description
Technical field
The present invention relates to magnesium alloy of a kind of metallic substance technical field and preparation method thereof, specifically, what relate to is cast magnesium alloys of a kind of Ag of containing and heavy rare earths and preparation method thereof.
Background technology
Along with world economy and human living standard's raising, the sustainable growth of automobile consumption, consequent tail gas pollution and energy pressure also increasingly sharpen, and the lightweight of automobile becomes the key and the inexorable trend of energy-saving and emission-reduction.In addition, also there is very intensive demand leading-edge fields such as aerospace, military project, racing car to lightweight, and can bring great economic benefit.In numerous light materials, magnesium alloy because of its extremely low density, good specific tenacity, damping property, castability and easily recovery property etc. be described as " 21 century tool development potentiality and the green engineering material of future ".Yet intensity that magnesium alloy is relatively low and plasticity have limited it and have used widely in these fields.At present, developed multiple serial high-strength magnesium alloys such as Mg-Al-Mn, Mg-Al-Zn, Mg-RE, wherein Mg-RE is the comparatively successful class high-strength magnesium alloy of development and application, as WE54, and QE22 etc.
Find that through literature search it is that alloy has excellent mechanical property that significant solid solution of Gd and Y and ageing strengthening ability make Mg-Gd-Y to prior art.The Mg-10Gd-2Y-0.5Zr alloy that S.M.He etc. report in " Microstructure and strengthening mechanism of high strengthMg-10Gd-2Y-0.5Zr alloy " (microtexture of high strength Mg-10Gd-2Y-0.5Zr alloy and strengthening mechanism) literary composition that " Journal of Alloys andCompounds " (alloy and compound journal) delivered on the 427 phase 316-323 pages or leaves in 2007 is higher a kind of of performance in the present cast magnesium alloys, but its content of rare earth is higher, and room temperature tensile strength under the as cast condition T6 state and unit elongation also only are 362MPa and 4.9%, can make the alloy temperature-room type plasticity low excessively and further improve intensity by increase Gd and Y content merely, and can increase alloy density and cost.X.Gao etc. pass through to add the Ag element in " Enhancedprecipitation-hardening in Mg-Gd alloys containing Ag and Zn " (Ag and Zn element are to the promotion of Mg-Gd alloy precipitating reinforcing effect) literary composition that " Scripta Materialia " (material wall bulletin) delivered on the phase 619-622 page or leaf in 2008 58, Mg-6Gd-0.6Zr magnesium alloy age hardening effect and peak hardness have been significantly improved, but do not add the relatively low Y element of cost and density, make full use of that Gd and the significant solid solution of Y element and ageing strengthening ability obtain more excellent mechanical property in the Mg-Gd-Y alloy system.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, cast magnesium alloys of a kind of Ag of containing and heavy rare earths and preparation method thereof is provided, by in the Mg-Gd alloy, adding Mg-Y and Mg-Zr master alloy and a small amount of Ag element, and optimization solid solution and aging technique parameter, be implemented in when reducing the alloy content of rare earth, obtain more high strength and good plasticity.
The present invention is achieved by the following technical solutions:
The cast magnesium alloys that contains Ag and heavy rare earths involved in the present invention, component that comprises and weight percentage thereof are: Gd 6-10%, Y 0.5-4%, Ag 0.2-3%, Zr 0.35-0.7%, impurity element are less than 0.02%, and surplus is Mg.
Described impurity, impurity element that it comprises and weight percentage are: Fe＜0.005%, Cu＜0.015%, Ni＜0.002%.
The preparation method of the cast magnesium alloys that contains Ag and heavy rare earths involved in the present invention comprises the steps:
The first step is calculated the weight percent that raw material needs according to the composition that adopts, and raw material is: magnesium ingot (massfraction of Mg content is greater than 99.9%), technical pure Ag or Mg-Ag master alloy, Mg-Gd, Mg-Y and Mg-Zr master alloy.
Second step, above raw material is carried out melting handles, at first in baking oven, be preheating to 180-240 ℃, then with magnesium ingot at flux protection or SF
6And CO
2Mixed gas protected heating down; after treating that magnesium ingot melts fully; add the Mg-Gd master alloy at 730-760 ℃; treating that the magnesium liquid temp gos up adds the Mg-Y master alloy after 730-760 ℃, adds the Mg-Zr master alloy at 780-800 ℃, spend 2-10 minute after; keep heated condition and in whipping process, add pure Ag or Mg-Ag master alloy; 780 ℃ of insulations after about 5-20 minute, constantly electrorefining 5-15 minute, refining process needed fully stirring then.Refining was left standstill 20-40 minute at 760-780 ℃ after finishing, and treated that magnesium liquid is cooled to 700-720 ℃ of skimming operation, with casting ladle casting or low-pressure casting.
Described SF
6And CO
2Mixed gas wherein contains 0.2% volume fraction SF
6
Described flux is meant that magnesium alloy smelting uses flux always, as the normal commercial RJ-2 flux that uses both at home and abroad etc.
In the 3rd step, the magnesium alloy that second step was obtained carries out solution treatment and ageing treatment, promptly the 450-520 ℃ of solution treatment of carrying out 4-20h, carries out the ageing treatment of 8-50h subsequently under 175-250 ℃ temperature.
Alloy of the present invention is by adding a small amount of Ag element and optimizing solid solution and the aging technique parameter, increase timeliness precipitated phase quantity and make its refinement, effectively strengthen solid solution and ageing strengthening effect, the strengthening effect of Gd and Y is not fully exerted, under the prerequisite that guarantees enough strengthening effects, can reduce the alloy content of rare earth to greatest extent or add more Y and replace Gd, thereby avoid the destruction of the especially too high Gd content of too high content of rare earth, and reduce cost the material temperature-room type plasticity; When Y/Gd is big in alloy, needs to add more Ag unit and usually effectively promote its ageing strengthening to guarantee excellent properties; Add Zr by the remarkable crystal grain thinning of heterogeneous forming core, strengthen the refined crystalline strengthening effect and improve alloy plasticity.Excellent specific properties such as by above principle and method, it is low to make alloy of the present invention have a content of rare earth, and the high and plasticity of intensity is good.
Technology of the present invention is simple, and content of rare earth is lower, has guaranteed good plasticity when improving alloy strength, and can obtain the combination of different premium propertiess by adjusting alloying constituent and thermal treatment process, satisfies the needs of various application occasions.With Mg-8.5Gd-3Y-1.5Ag-0.35Zr (weight percent) alloy is example, and after Overheating Treatment, room temperature tensile strength reaches 420MPa, and unit elongation is 6.8%, far above the 280MPa of WE54, and 4% and the 370MPa of GW103K, 4.1%.
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.
Example 1:
Alloying constituent (weight percent) is: 10% Gd, 0.5% Y, 0.2% Ag, 0.5% Zr, impurity element are less than 0.02%, and all the other are Mg.
The melting technology of alloy is: according to mentioned component configuration alloy; in baking oven with raw material preheating to 180 ℃; in the resistance crucible furnace, add pure magnesium 14.7Kg then; under the protection of RJ-2 flux, heat; after treating that magnesium ingot melts fully; add 12.7Kg Mg-25% Gd master alloy at 730 ℃; treat that the rise of magnesium liquid temp adds 0.9Kg Mg-25% Y master alloy after 730 ℃; add Mg-30% Zr master alloy 1.7Kg at 780 ℃; after spending 2 minutes, keep heated condition and in whipping process, add pure Ag 0.06Kg, then about 5 minutes of 780 ℃ of insulations; constantly electrorefining is 10 minutes, and refining process needs fully to stir.Refining was left standstill 40 minutes at 760 ℃ after finishing, and treated that magnesium liquid is cooled to 700 ℃ of skimming operations, with casting ladle casting or low-pressure casting.
This example alloy solid solution treatment process is 450 ℃, 20h, and through 175 ℃, after the 40h ageing treatment, room temperature tensile strength is that 386MPa, yield strength are that 235MPa, unit elongation are 8.2%; Through 200 ℃, after the 24h ageing treatment, room temperature tensile strength is that 360MPa, yield strength are that 206MPa, unit elongation are 10.3%.
Example 2:
Alloying constituent (weight percent) is: 8.5% Gd, 3% Y, 1.5% Ag, 0.35% Zr, impurity element are less than 0.02%, and all the other are Mg.
The melting technology of alloy is: according to mentioned component configuration alloy, with raw material preheating to 200 ℃, add pure magnesium 12.3Kg then in the resistance crucible furnace in baking oven, containing 0.2% volume fraction SF
6SF
6And CO
2Mixed gas protected heating down; after treating that magnesium ingot melts fully; add 10.8Kg Mg-25% Gd master alloy at 740 ℃; treat that the rise of magnesium liquid temp adds 5.2Kg Mg-25% Y master alloy after 740 ℃, add Mg-30% Zr master alloy 1.2Kg at 790 ℃, excessively after 5 minutes; keep heated condition and in whipping process, add pure Ag 0.5Kg; about 10 minutes of 780 ℃ of insulations, constantly electrorefining was 10 minutes then, and refining process needs fully to stir.Refining was left standstill 30 minutes at 770 ℃ after finishing, and treated that magnesium liquid is cooled to 710 ℃ of skimming operations, with casting ladle casting or low-pressure casting.
This example alloy solid solution treatment process is 520 ℃, 4h, and through 225 ℃, after the 24h ageing treatment, room temperature tensile strength is that 420MPa, yield strength are that 264MPa, unit elongation are 6.8%; Through 250 ℃, after the 8h ageing treatment, room temperature tensile strength is that 394MPa, yield strength are that 232MPa, unit elongation are 8.9%.
Example 3:
Alloying constituent (weight percent) is: 7.5% Gd, 2% Y, 2.0% Ag, 0.6% Zr, impurity element are less than 0.02%, and all the other are Mg.
The melting technology of alloy is: according to mentioned component configuration alloy, with raw material preheating to 220 ℃, add pure magnesium 12.5Kg then in the resistance crucible furnace in baking oven, containing 0.2% volume fraction SF
6SF
6And CO
2The protection of mixed gas is heating down; after treating that magnesium ingot melts fully; add 9.5Kg Mg-25% Gd master alloy at 750 ℃; treat that the rise of magnesium liquid temp adds 3.5Kg Mg-25% Y master alloy after 750 ℃, add Mg-30% Zr master alloy 2Kg at 800 ℃, excessively after 8 minutes; keep heated condition and in whipping process, add Mg-25% Ag master alloy 2.5Kg; about 15 minutes of 780 ℃ of insulations, constantly electrorefining was 15 minutes then, and refining process needs fully to stir.Refining was left standstill 20 minutes at 780 ℃ after finishing, and treated that magnesium liquid is cooled to 720 ℃ of skimming operations, with casting ladle casting or low-pressure casting.
This example alloy solid solution treatment process is 480 ℃, 12h, and through 200 ℃, after the 32h ageing treatment, room temperature tensile strength is that 402MPa, yield strength are that 238MPa, unit elongation are 10.4%; Through 225 ℃, after the 12h ageing treatment, room temperature tensile strength is that 387MPa, yield strength are that 211MPa, unit elongation are 14.8%.
Example 4:
Alloying constituent (weight percent) is: 6% Gd, 4% Y, 3% Ag, 0.7% Zr, impurity element are less than 0.02%, and all the other are Mg.
The melting technology of alloy is: according to mentioned component configuration alloy; in baking oven with raw material preheating to 240 ℃; in the resistance crucible furnace, add pure magnesium 12.2Kg then; under the RJ-2 flux protection, heat; after treating that magnesium ingot melts fully; add 7.6Kg Mg-25% Gd master alloy at 760 ℃; treat that the rise of magnesium liquid temp adds 6.9Kg Mg-25% Y master alloy after 760 ℃; add Mg-30% Zr master alloy 2.4Kg at 800 ℃; after spending 2 minutes, keep heated condition and in whipping process, add pure Ag 0.9Kg, then about 20 minutes of 780 ℃ of insulations; constantly electrorefining is 5 minutes, and refining process needs fully to stir.Refining was left standstill 20 minutes at 780 ℃ after finishing, and treated that magnesium liquid is cooled to 720 ℃ of skimming operations, with casting ladle casting or low-pressure casting.
This example alloy solid solution treatment process is 500 ℃, 8h, and through 200 ℃, after the 50h ageing treatment, room temperature tensile strength is that 407MPa, yield strength are that 247MPa, unit elongation are 9.5%; Through 225 ℃, after the 16h ageing treatment, room temperature tensile strength is that 381MPa, yield strength are that 213MPa, unit elongation are 11.3%.
Claims (8)
1, a kind of cast magnesium alloys that contains Ag and heavy rare earths is characterized in that the component and the weight percentage thereof that comprise are: Gd 6-10%, and Y 0.5-4%, Ag 0.2-3%, Zr 0.35-0.7%, impurity element are less than 0.02%, and surplus is Mg.
2, the cast magnesium alloys that contains Ag and heavy rare earths according to claim 1 is characterized in that, described impurity, and element that it comprises and weight percentage are: Fe＜0.005%, Cu＜0.015%, Ni＜0.002%.
3, a kind of preparation method who contains the cast magnesium alloys of Ag and heavy rare earths as claimed in claim 1 is characterized in that comprising the steps:
The first step is calculated the weight percent that raw material needs according to the composition that adopts, and raw material is a magnesium ingot, technical pure Ag or Mg-Ag master alloy, Mg-Gd, Mg-Y and Mg-Zr master alloy;
Second step, above raw material is carried out melting to be handled, at first in baking oven, be preheating to 180-240 ℃, then magnesium ingot is heated, after treating that magnesium ingot melts fully, add the Mg-Gd master alloy at 730-760 ℃, treat that the magnesium liquid temp gos up and after 730-760 ℃, add the Mg-Y master alloy, add the Mg-Zr master alloy at 780-800 ℃, after spending 2-10 minute, keep heated condition also in whipping process, to add pure Ag or Mg-Ag master alloy, then 780 ℃ of insulations after 5-20 minute, refining 5-15 minute, after refining finishes, left standstill 20-40 minute at 760-780 ℃, treat that magnesium liquid is cooled to 700-720 ℃ of skimming operation, with casting ladle casting or low-pressure casting;
In the 3rd step, the magnesium alloy that second step was obtained carries out solution treatment and ageing treatment, promptly the 450-520 ℃ of solution treatment of carrying out 4-20h, carries out the ageing treatment of 8-50h subsequently under 175-250 ℃ temperature.
4, the preparation method who contains the cast magnesium alloys of Ag and heavy rare earths according to claim 3 is characterized in that, the massfraction of Mg content is greater than 99.9% in the described magnesium ingot.
5, the preparation method who contains the cast magnesium alloys of Ag and heavy rare earths according to claim 3 is characterized in that, and is described with the magnesium ingot heating, is meant magnesium ingot at flux protection or SF
6And CO
2Mixed gas protected heating down.
6, the preparation method who contains the cast magnesium alloys of Ag and heavy rare earths according to claim 5 is characterized in that, described flux is meant RJ-2.
7, the preparation method who contains the cast magnesium alloys of Ag and heavy rare earths according to claim 5 is characterized in that, described SF
6And CO
2Mixed gas wherein contains 0.2% volume fraction SF
6
8, the preparation method who contains the cast magnesium alloys of Ag and heavy rare earths according to claim 3 is characterized in that, stirs simultaneously in the described refining process.
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| CN104152771A (en) * | 2014-07-29 | 2014-11-19 | 李克杰 | Silver and rare earth-containing high-strength heat-resistant magnesium alloy and preparation method thereof |
| CN104152772A (en) * | 2014-07-29 | 2014-11-19 | 李克杰 | Silver/strontium/rare-earth-containing high-strength heat-resistant magnesium alloy and preparation method thereof |
| CN104498797A (en) * | 2014-12-31 | 2015-04-08 | 上海交通大学 | High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy |
| CN104988371A (en) * | 2015-06-16 | 2015-10-21 | 上海交通大学 | Rear-earth magnesium alloy suitable for sand mould casting and preparation method for rear-earth magnesium alloy |
| CN105624504A (en) * | 2016-02-03 | 2016-06-01 | 中南大学 | Heat-resisting rare earth magnesium alloy and thermal treatment process for uneven-wall-thickness casting of heat-resisting rare earth magnesium alloy |
| CN105648370A (en) * | 2016-02-03 | 2016-06-08 | 中南大学 | Heat treatment technology for improving mechanical properties of rare earth magnesium alloy castings |
| CN106048269A (en) * | 2016-07-25 | 2016-10-26 | 北京工业大学 | Method for preparing large nanocrystalline magnesium alloy through small deformation |
| CN107022707A (en) * | 2017-03-23 | 2017-08-08 | 中南大学 | A kind of big component Technology for Heating Processing of strong high temperature resistant magnesium alloy of superelevation |
| CN107034402A (en) * | 2017-03-23 | 2017-08-11 | 中南大学 | The big ingot blank electromagnetism semicontinuous casting technique of the strong high temperature resistant magnesium alloy of superelevation |
| CN107245619A (en) * | 2017-03-03 | 2017-10-13 | 中南大学 | A kind of strong high temperature resistant magnesium alloy of superelevation |
| CN108707848A (en) * | 2018-07-07 | 2018-10-26 | 中南大学 | A kind of VW93M nanometers of isomery magnesium alloy aging thermal treating process |
| CN108707803A (en) * | 2018-07-07 | 2018-10-26 | 中南大学 | A kind of VW93M nanometer Mgs alloy aging heat treatment process |
| CN108715965A (en) * | 2018-07-07 | 2018-10-30 | 中南大学 | A kind of atom segregation and elementide strengthen VW93M magnesium alloy methods |
| CN108728714A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of strong nanometer isomery magnesium alloy preparation method of VW93M superelevation |
| CN108728710A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of strong nanometer gradient magnesium alloy preparation method of VW93M superelevation |
| CN108728715A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of powerful block nanometer magnesium alloy preparation method of VW93M superelevation |
| CN108754366A (en) * | 2018-07-07 | 2018-11-06 | 中南大学 | A kind of high thermal stability VW93M nanometers of magnesium alloy preparation methods |
| CN112410632A (en) * | 2020-11-20 | 2021-02-26 | 中国科学院长春应用化学研究所 | Mg-Gd-Y-Nd high-strength rare earth magnesium alloy and preparation method thereof |
| CN113913660A (en) * | 2021-09-03 | 2022-01-11 | 北京工业大学 | Method for preparing magnesium alloy plate by hot-cold alternative rolling |
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- 2009-01-15 CN CNA2009100454094A patent/CN101463442A/en active Pending
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| CN104152772A (en) * | 2014-07-29 | 2014-11-19 | 李克杰 | Silver/strontium/rare-earth-containing high-strength heat-resistant magnesium alloy and preparation method thereof |
| CN104152771A (en) * | 2014-07-29 | 2014-11-19 | 李克杰 | Silver and rare earth-containing high-strength heat-resistant magnesium alloy and preparation method thereof |
| CN104152771B (en) * | 2014-07-29 | 2017-02-15 | 李克杰 | Silver and rare earth-containing high-strength heat-resistant magnesium alloy and preparation method thereof |
| CN104498797A (en) * | 2014-12-31 | 2015-04-08 | 上海交通大学 | High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy |
| CN104988371B (en) * | 2015-06-16 | 2018-02-09 | 上海交通大学 | Magnesium-rare earth suitable for sand casting and preparation method thereof |
| CN104988371A (en) * | 2015-06-16 | 2015-10-21 | 上海交通大学 | Rear-earth magnesium alloy suitable for sand mould casting and preparation method for rear-earth magnesium alloy |
| CN105624504A (en) * | 2016-02-03 | 2016-06-01 | 中南大学 | Heat-resisting rare earth magnesium alloy and thermal treatment process for uneven-wall-thickness casting of heat-resisting rare earth magnesium alloy |
| CN105648370A (en) * | 2016-02-03 | 2016-06-08 | 中南大学 | Heat treatment technology for improving mechanical properties of rare earth magnesium alloy castings |
| CN106048269B (en) * | 2016-07-25 | 2018-02-23 | 北京工业大学 | A kind of method that small deformation amount prepares bulk nanocrystalline magnesium alloy |
| CN106048269A (en) * | 2016-07-25 | 2016-10-26 | 北京工业大学 | Method for preparing large nanocrystalline magnesium alloy through small deformation |
| CN107245619A (en) * | 2017-03-03 | 2017-10-13 | 中南大学 | A kind of strong high temperature resistant magnesium alloy of superelevation |
| CN107245619B (en) * | 2017-03-03 | 2018-08-10 | 中南大学 | A kind of strong high temperature resistant magnesium alloy of superelevation |
| CN107034402A (en) * | 2017-03-23 | 2017-08-11 | 中南大学 | The big ingot blank electromagnetism semicontinuous casting technique of the strong high temperature resistant magnesium alloy of superelevation |
| CN107022707A (en) * | 2017-03-23 | 2017-08-08 | 中南大学 | A kind of big component Technology for Heating Processing of strong high temperature resistant magnesium alloy of superelevation |
| CN107034402B (en) * | 2017-03-23 | 2018-08-07 | 中南大学 | The big ingot blank electromagnetism semicontinuous casting technique of the strong high temperature resistant magnesium alloy of superelevation |
| CN108715965A (en) * | 2018-07-07 | 2018-10-30 | 中南大学 | A kind of atom segregation and elementide strengthen VW93M magnesium alloy methods |
| CN108707803A (en) * | 2018-07-07 | 2018-10-26 | 中南大学 | A kind of VW93M nanometer Mgs alloy aging heat treatment process |
| CN108707848A (en) * | 2018-07-07 | 2018-10-26 | 中南大学 | A kind of VW93M nanometers of isomery magnesium alloy aging thermal treating process |
| CN108728714A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of strong nanometer isomery magnesium alloy preparation method of VW93M superelevation |
| CN108728710A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of strong nanometer gradient magnesium alloy preparation method of VW93M superelevation |
| CN108728715A (en) * | 2018-07-07 | 2018-11-02 | 中南大学 | A kind of powerful block nanometer magnesium alloy preparation method of VW93M superelevation |
| CN108754366A (en) * | 2018-07-07 | 2018-11-06 | 中南大学 | A kind of high thermal stability VW93M nanometers of magnesium alloy preparation methods |
| CN112410632A (en) * | 2020-11-20 | 2021-02-26 | 中国科学院长春应用化学研究所 | Mg-Gd-Y-Nd high-strength rare earth magnesium alloy and preparation method thereof |
| CN112410632B (en) * | 2020-11-20 | 2022-03-08 | 中国科学院长春应用化学研究所 | Mg-Gd-Y-Nd high-strength rare earth magnesium alloy and preparation method thereof |
| CN113913660A (en) * | 2021-09-03 | 2022-01-11 | 北京工业大学 | Method for preparing magnesium alloy plate by hot-cold alternative rolling |
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