CN101481766A - Mn-Al intermediate alloy, and preparation and use thereof - Google Patents
Mn-Al intermediate alloy, and preparation and use thereof Download PDFInfo
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- CN101481766A CN101481766A CNA2008101824535A CN200810182453A CN101481766A CN 101481766 A CN101481766 A CN 101481766A CN A2008101824535 A CNA2008101824535 A CN A2008101824535A CN 200810182453 A CN200810182453 A CN 200810182453A CN 101481766 A CN101481766 A CN 101481766A
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Abstract
The invention relates to a Mn-Al binary intermediate alloy which can thin a magnesium alloy, particularly solidified crystal grains of Mg-Mn alloy series and Mg-Zn alloy series, and a preparation method and the application thereof. The intermediate alloy comprises 65-75wt% of Mn and 35-25wt% of Al; the intermediate alloy is mainly produced through various spray casting methods; the alloy solidification speed is about 10<3-6> DEGC/s; the intermediate alloy comprises Epsilon-MnAl phase and Gamma-Al8Mn5 phase, but not Al at free state; and the intermediate alloy can lead different magnesium alloys to obtain different thinning effects of solidified crystal grains.
Description
Technical field
The present invention relates to Mn-Al master alloy, its preparation method and be used for the refinement magnesium alloy especially refinement Mg-Mn system be the purposes of alloy graining crystal grain with Mg-Zn.The invention belongs to magnesium alloy materials solidification technology field.
Background technology
Especially Mg-Mn system and Mg-Zn are that the research and development of the master alloy of alloy graining crystal grain are the problems that people pay close attention to always to be used for the refinement magnesium alloy.But except the Mg-Zr master alloy that is exclusively used in refinement Mg-Zn system, not having other to can be used for refinement Mg-Mn system as yet is the successful report of master alloy research and development of alloy graining crystal grain with Mg-Zn at present.
The master alloy that is used for refinement Mg-Mn system and Mg-Zn and is alloy graining crystal grain can not contain the Al of free state, and this is because the Al of free state can be the Zr reaction that contains usually in the alloy with Mg-Zn, and forms Al in melt
3Zr is the refinement of alloy graining crystal grain to Mg-Zn thereby weaken or destroy Zr; Same is in the thinning process of alloy graining crystal grain at Mg-Mn, can not contain the Al of free state, and this is because the Al of free state can react with Mn, forms the aluminium manganic compound, is a series of performances of alloy thereby destroy Mg-Mn.
In addition, though for refinement Mg-Zn is that the existing Mg-Zr master alloy of alloy graining crystal grain can utilize, but be that preparation Mg-Zr master alloy also is to use the Mg-Zr master alloy all to have a series of problem not solve fully, this is to contain the high and uniform master alloy of composition of Zr amount because be difficult to preparation on the one hand, Mg-Zr master alloy production technique more complicated on the other hand, seriously polluted, and also often exist Zr to be deposited to the phenomenon of furnace bottom when using the Mg-Zr master alloy.For refinement Mg-Mn is alloy graining crystal grain, at present just without any adaptable master alloy; Only contain Al even have as Mg-Al-C
4C
3The master alloy that does not contain free state Al mutually, but Al
4C
3Phase structure is subject to the destruction of Mn, thereby on the one hand destroys grain refining effect, and also weakening Mn on the other hand is effect in the alloy at Mg-Mn.
Summary of the invention
The present invention has invented a kind of Mn-Al binary master alloy for solving above-mentioned series of technical, and it is characterized in that: this alloy comprises the Mn of 65～75wt% and the Al of 35～25wt%.
Mn-Al master alloy according to the present invention preferably contains ε-MnAl phase and γ
/-Al
8Mn
5Phase, but free state Al do not contained.According to ε-MnAl in the Mn-Al master alloy of the present invention is the close-packed hexagonal structure phase mutually, and lattice lattice constant (a=0.2897nm) is very close with Mg (a=0.3200nm).
Mn-Al master alloy according to the present invention can be used for the various magnesium alloy of refinement especially to a certain extent refinement Mg-Mn be alloy graining crystal grain.
According to Mn-Al master alloy of the present invention preferably mainly is to produce with the spray to cast method.
The invention still further relates to a kind of method that is used to prepare described Mn-Al binary master alloy, it is characterized in that: the Mn of 65～75 weight parts is mixed melting in the crucible of packing into the Al of 35～25 weight parts, carry out spray to cast after alloy melting is complete, setting rate is 10
3～6℃/s.
According to a preferred scheme of the inventive method, described crucible is the high-frequency induction smelting pot that has protection of inert gas.
According to a preferred scheme of the inventive method, in the spray to cast process, use water cooled copper mould as mold, also can use the copper list roller of high speed rotating or the two rollers of copper as mold.
The method according to this invention particularly preferably may further comprise the steps:
1. press mass ratio Mn:Al=(65～75): good Mn of (35～25) weighing and Al.
2. Mn is mixed with Al and insert melting in the high-frequency induction smelting pot that has protection of inert gas.This crucible can be the silica tube with flat or round nozzle.
3. alloy melting carries out spray to cast after fully, and the spray to cast temperature is about 1400 ℃.The mold of spray to cast can be a water cooled copper mould, also can be the copper list roller or the two rollers of copper of high speed rotating.Setting rate is 10
3～6℃/s about.
4. be that the strip of spray to cast moulding is laminar as fruit product, then suitably cut the equivalent packing; If the ingot shape of spray to cast moulding is then cut apart the equivalent packing; By industrial use habit, the quality of each packing is that 100～1000g does not wait.
The using method of the Mn-Al master alloy of introducing among the present invention and all kinds of grain refinings do not have different with the using method of master alloy, promptly directly master alloy is added in fusing or the holding furnace and stirs according to adding proportion to get final product.
Description of drawings
Fig. 1 is the microstructure of the Mn-28%Al alloy of spray to cast, and wherein strip is ε-MnAl phase with herring-bone form mutually mutually, and all the other are γ
/-Al
8Mn
5Phase.
Fig. 2 is the X-ray diffraction spectrum of the Mn-28%Al alloy of spray to cast, through demarcating, wherein contains ε-MnAl phase and γ really
/-Al
8Mn
5Phase.
Fig. 3 (a), 3 (b) solidify macroscopical comparison diagram of grain size before and after Mn-28%Al master alloy thinning processing for pure Mg, the macroscopic view of pure Mg before Fig. 3 (a) expression thinning processing is solidified grain size, and the macroscopic view of the Mg+0.4wt%Mn-28wt%Al after Fig. 3 (b) expression thinning processing is solidified grain size.
Fig. 4 (a), 4 (b) are macroscopical comparison diagram of AZ31 alloy alloy graining grain size before and after Mn-28%Al master alloy thinning processing of Mg-Al system, wherein the macroscopic view of the AZ31 alloy before Fig. 4 (a) expression thinning processing is solidified grain size, and the macroscopic view of the AZ31+0.4wt%Mn-28wt%Al after Fig. 4 (b) expression thinning processing is solidified grain size.
Fig. 5 (a), 5 (b) are macroscopical comparison diagram of Mg-1%Mn alloy alloy graining grain size before and after Mn-28%Al master alloy thinning processing of Mg-Mn system, wherein the macroscopic view of the Mg-1%Mn before Fig. 5 (a) expression thinning processing is solidified grain size, and the macroscopic view of the Mg-1%Mn+0.4wt%Mn-28wt%Al after Fig. 5 (b) expression thinning processing is solidified grain size.
Fig. 6 (a), 6 (b) are macroscopical comparison diagram of Mg-4%Zn alloy alloy graining grain size before and after Mn-28%Al master alloy thinning processing of Mg-Zn system, wherein the macroscopic view of the Mg-4%Zn before Fig. 6 (a) expression thinning processing is solidified grain size, and the macroscopic view of the Mg-4%Zn+0.4wt%Mn-28wt%AL after Fig. 6 (b) expression thinning processing is solidified grain size.
Embodiment
1. press good Mn sheet of mass ratio Mn:Al=72:28 weighing and aluminium flake, and the Mn sheet mixed with aluminium flake be contained in the silica tube, then under protection of inert gas with the alloy in the high frequency induction power supply heating smelting quartz pipe, after melting is intact the melt spray to cast is gone into diameter of bore and is
(speed of cooling is 10 in continuous cooling in the water cooled copper mould of 8-10mm
5℃/s about), cooling finishes, and takes out alloy, is one of form of alloy of the present invention.
2. press good Mn sheet of mass ratio Mn:Al=70:30 weighing and aluminium flake; and the Mn sheet mixed with aluminium flake be contained in the silica tube; then under protection of inert gas with the alloy in the high frequency induction power supply heating smelting quartz pipe, after melting is intact melt spray to cast (being referred to as to get rid of band usually) cooled off continuously on the copper list roller of high speed rotating that (speed of cooling is 10
5℃/s about), spray to cast finishes, and obtains discontinuous, band, sheet alloy, is one of form of alloy of the present invention.
3. press good Mn sheet of mass ratio Mn:Al=68:32 weighing and aluminium flake; and the Mn sheet mixed with aluminium flake be contained in the silica tube; then under protection of inert gas with the alloy in the high frequency induction power supply heating smelting quartz pipe, after melting is intact with the melt spray to cast on the two rollers of the copper of a pair of high speed rotating in opposite directions continuously cooling (speed of cooling is 10
6℃/s about), spray to cast finishes, and obtains discontinuous, band, sheet alloy, is one of form of alloy of the present invention.
4. the Mn-28%Al master alloy with the spray to cast moulding adds pure Mg melt, and the master alloy add-on is the 0.2-0.8% of pure Mg quality, adds the smelting temperature that temperature is equal to pure Mg.It solidifies grain refining effect shown in Fig. 3 (b), wherein Fig. 3 (a) when not adding the Mn-28%Al master alloy under the same curing condition pure Mg solidify grain size.
5. the Mn-28%Al master alloy of spray to cast moulding is added the AZ31 alloy of Mg-Al system, add-on is the 0.2-0.8% of AZ31 alloy mass, adds the smelting temperature that temperature is equal to the AZ31 alloy.It solidifies grain refining effect shown in Fig. 4 (b), wherein Fig. 4 (a) when not adding the Mn-28%Al master alloy AZ31 alloy solidify grain size.When not adding master alloy under the different curing conditions grain size of solidifying of AZ31 alloy have nothing in common with each other, flourishing column crystal is arranged, have, setting rate little because of ingot casting soon to a certain extent refinement.Only represented relative grain-size herein, down together.
6. the Mn-28%Al master alloy adding Mg-Mn with the spray to cast moulding is an alloy, and it is 1% that alloy contains the Mn amount, and the master alloy add-on is the 0.2-0.8% of Mg-Mn alloy mass, adds the smelting temperature that temperature is equal to the Mg-Mn alloy.It solidifies grain refining effect shown in Fig. 5 (b), wherein Fig. 5 (a) when not adding the Mn-28%Al master alloy under the same curing condition Mg-Mn alloy solidify grain size.
7. the Mn-28%Al master alloy adding Mg-Zn with the spray to cast moulding is an alloy, and it is 5% that alloy contains the Zn amount, and alloy does not contain Zr, and the master alloy add-on is the 0.2-0.8% of Mg-Zn alloy mass, adds the smelting temperature that temperature is equal to the Mg-Zn alloy.It solidifies grain refining effect shown in Fig. 6 (b), wherein Fig. 6 (a) when not adding the Mn-28%Al master alloy under the same curing condition Mg-Zn alloy solidify grain size.
Claims (9)
1. Mn-Al binary master alloy, it is characterized in that: this alloy comprises the Mn of 65～75wt% and the Al of 35～25wt%.
2. Mn-Al binary master alloy according to claim 1 is characterized in that: this alloy contain ε-MnAl mutually and γ/-Al
8Mn
5Phase, but free state Al do not contained.
3. Mn-Al binary master alloy according to claim 1 and 2 is characterized in that: this alloy mainly is to produce with the spray to cast method.
4. be used to prepare method according to the described Mn-Al binary of one of claim 1 to 3 master alloy, it is characterized in that: the Mn of 65～75 weight parts is mixed melting in the crucible of packing into the Al of 35～25 weight parts, carry out spray to cast after alloy melting is complete, setting rate is 10
3～6℃/s.
5. 4 described methods as requested, it is characterized in that: described crucible is the high-frequency induction smelting pot that has protection of inert gas.
6. 4 or 5 described methods as requested is characterized in that: use water cooled copper mould as mold in described spray to cast process.
7. 4 or 5 described methods as requested is characterized in that: use the copper list roller of high speed rotating or the two rollers of copper as mold in described spray to cast process.
8. the purposes of solidifying crystal grain that is used for the refinement magnesium alloy according to the described Mn-Al binary of one of claim 1 to 3 master alloy.
9. purposes according to claim 8 is characterized in that: described magnesium alloy comprises that Mg-Mn is that alloy and Mg-Zn are alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824535A CN101481766B (en) | 2008-12-08 | 2008-12-08 | Mn-Al intermediate alloy, and preparation and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824535A CN101481766B (en) | 2008-12-08 | 2008-12-08 | Mn-Al intermediate alloy, and preparation and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101481766A true CN101481766A (en) | 2009-07-15 |
| CN101481766B CN101481766B (en) | 2012-01-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693969B (en) * | 2009-10-14 | 2011-05-25 | 东北大学 | Mg-Al-based alloy Al-Mn grain refiner, preparation method and using method thereof |
| CN104195359A (en) * | 2014-07-16 | 2014-12-10 | 沈阳航空航天大学 | High-manganese-content aluminum-manganese intermediate alloy and manufacturing method thereof |
| CN106062224A (en) * | 2014-04-10 | 2016-10-26 | 韩国机械研究院 | Crystal grain refiner for magnesium alloy, containing aluminum, a method for preparing magnesium alloy, and magnesium alloy manufactured by same method |
| CN106997800A (en) * | 2017-03-10 | 2017-08-01 | 杭州电子科技大学 | One kind is without rare earth MnAlCuC permanent-magnet alloys and preparation method thereof |
| WO2021143013A1 (en) * | 2020-01-16 | 2021-07-22 | 深圳市新星轻合金材料股份有限公司 | Manganese aluminum alloy and preparation method therefor |
-
2008
- 2008-12-08 CN CN2008101824535A patent/CN101481766B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693969B (en) * | 2009-10-14 | 2011-05-25 | 东北大学 | Mg-Al-based alloy Al-Mn grain refiner, preparation method and using method thereof |
| CN106062224A (en) * | 2014-04-10 | 2016-10-26 | 韩国机械研究院 | Crystal grain refiner for magnesium alloy, containing aluminum, a method for preparing magnesium alloy, and magnesium alloy manufactured by same method |
| CN106062224B (en) * | 2014-04-10 | 2018-02-06 | 韩国机械研究院 | The manufacture method of grain refiner for magnesium alloy, magnesium alloy comprising aluminium and the magnesium alloy using this method manufacture |
| CN104195359A (en) * | 2014-07-16 | 2014-12-10 | 沈阳航空航天大学 | High-manganese-content aluminum-manganese intermediate alloy and manufacturing method thereof |
| CN106997800A (en) * | 2017-03-10 | 2017-08-01 | 杭州电子科技大学 | One kind is without rare earth MnAlCuC permanent-magnet alloys and preparation method thereof |
| CN106997800B (en) * | 2017-03-10 | 2018-12-07 | 杭州电子科技大学 | A kind of no rare earth MnAlCuC permanent-magnet alloy and preparation method thereof |
| WO2021143013A1 (en) * | 2020-01-16 | 2021-07-22 | 深圳市新星轻合金材料股份有限公司 | Manganese aluminum alloy and preparation method therefor |
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| Publication number | Publication date |
|---|---|
| CN101481766B (en) | 2012-01-18 |
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