EP2481822B1 - Legierung auf Magnesium-Aluminium-Basis mit Kornverfeiner - Google Patents

Legierung auf Magnesium-Aluminium-Basis mit Kornverfeiner Download PDF

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Publication number
EP2481822B1
EP2481822B1 EP11152825.3A EP11152825A EP2481822B1 EP 2481822 B1 EP2481822 B1 EP 2481822B1 EP 11152825 A EP11152825 A EP 11152825A EP 2481822 B1 EP2481822 B1 EP 2481822B1
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EP
European Patent Office
Prior art keywords
magnesium
grain
aluminum
grain refiner
aluminum alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP11152825.3A
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English (en)
French (fr)
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EP2481822A1 (de
Inventor
Yuanding Huang
Qiuming Peng
Norbert Hort
Karl Ulrich Kainer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Application filed by Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH filed Critical Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
Priority to EP11152825.3A priority Critical patent/EP2481822B1/de
Priority to ES11152825T priority patent/ES2424005T3/es
Priority to US13/352,632 priority patent/US20120195789A1/en
Priority to CA2765465A priority patent/CA2765465A1/en
Priority to CN201210022182.3A priority patent/CN102628133B/zh
Publication of EP2481822A1 publication Critical patent/EP2481822A1/de
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Publication of EP2481822B1 publication Critical patent/EP2481822B1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20—Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent

Definitions

  • the present invention relates to magnesium-aluminum based alloys having a small grain size and to a method of their production.
  • the alloys are particularly useful in casting applications.
  • Magnesium alloy developments have traditionally been driven by aerospace industry requirements for lightweight materials to operate under increasingly demanding conditions. Magnesium alloys have always been attractive to designers due to their low density, only two thirds that of aluminium. This has been a major factor in the widespread use of magnesium alloy castings and wrought products.
  • a small grain size generally accounts for improved mechanical properties and structural uniformity of magnesium alloys, resulting in better machinability, good resistance to hot tearing and superior extrudability. Numerous components are produced by extrusion, rolling or forging from cast billets. Thus, a small grain size of magnesium alloys in casting is important not only for the service performance of as-cast products but also for the components which are necessary for performing the secondary processing.
  • magnesium alloys can be classified into two broad groups: aluminum free and aluminum bearing magnesium alloys.
  • Aluminum-free alloys mainly refer to those containing zinc or grain refined by zirconium such as ZE41, ZK60, WE43 and EZ33. In these alloys, the grain sizes can be controlled and reduced by adding zirconium.
  • the exceptional grain-refining ability of zirconium does not function in aluminum bearing alloys such as AM50, AM60, and AZ91, as aluminum and zirconium can readily interact to form stable intermetallic phases, which are unfortunately ineffective as nucleants for magnesium grains. Therefore, a suitable grain refiner for magnesium-aluminum alloys is still desirable.
  • the magnesium alloys are heated to around 150 to 250°C above their melting point, maintained at that temperature for 5 to 15 minutes, and then rapidly cooled to the casting temperature.
  • the grain refining mechanism was suggested to be a heterogeneous nucleation by an Al-Mn-Fe compound.
  • Carbon inoculation is another major and effective grain refining approach developed to date for magnesium-aluminum based alloys.
  • the key step of this process is the introduction of carbon into the molten magnesium.
  • the grain refining mechanism is said to be heterogeneous nucleation by aluminum carbide (Al 4 C 3 ) produced by carbon in the compound reacting with aluminum in the melt.
  • Al 4 C 3 aluminum carbide
  • C 7 Cl 6 was added as a grain refiner, but this is no longer allowed because it produces harmful gases.
  • the inorganic carbon, such as graphite, carbon and wax were investigated as a grain refiner. However, their effects on the grain refinement are limited.
  • ferric chloride is added to a melt at around 760°C, and the melt is at this temperature maintained for 30 to 60 minutes, giving rise to the formation of an Al-Mn-Fe compound that was said to produce the grain refinement. It has been reported that in order to obtain a pronounced refinement effect, the manganese content has to be above a critical value. The problem with this method is the deterioration of corrosion resistance caused by a localized battery effect of the Fe and Mn.
  • the present invention provides a magnesium-aluminum alloy comprising a grain refiner, the grain refiner having the chemical formula: Mg 100-x-y-z Al x C y R z wherein R is an element selected from the group consisting of silicon, calcium, or strontium , x is from 10 to 50 At.%, y is from 10 to 35 At.%, and z is from 1 to 20 At.%, provided that x+y+z is less than 100 At.%. Preferably, x is from 20 to 50 At.%.
  • the magnesium-aluminum alloy preferably comprises the grain refiner in an added amount of 0.1 to 2% by weight of the initial weight of the alloy.
  • the magnesium-aluminum alloy can be any conventional alloy comprising magnesium and aluminum.
  • the magnesium-aluminum alloy is selected from the group consisting of magnesium-aluminum-zinc alloys and magnesium-aluminum-manganese alloys, more preferably, the alloy is selected from the group consisting of AM50, AM60, AM201, AZ10, AZ31, AZ63, AZ80 and AZ91.
  • the present invention provides a method for producing a magnesium-aluminum alloy having fine grain, which comprises melting an alloy comprising magnesium and aluminum under a protective gas atmosphere, adding to the molten magnesium-aluminum alloy a grain refiner having the chemical formula: Mg 100-x-y-z Al x C y R z wherein R is an element selected from the group consisting of silicon, calcium, or strontium, x is from 10 to 50 At.%, y is from 10 to 35 At.%, and z is from 1 to 20 At.%, provided that x+y+z is less than 100 At.%, and allowing the alloy to solidify.
  • the magnesium-aluminum alloy preferably comprises the grain refiner in an added amount of 0.1 to 2% by weight of the initial weight of the alloy.
  • the magnesium-aluminum alloy can be any conventional alloy comprising magnesium and aluminum.
  • the magnesium-aluminum alloy is selected from the group consisting of magnesium-aluminum-zinc alloys and magnesium-aluminum-manganese alloys, more preferably, the alloy is selected from the group consisting of AM50, AM60, AM201, AZ10, AZ31, AZ63, AZ80, AZ91, AE44, AE42, AJ53, AS41 and AS42.
  • the molten magnesium-aluminum alloy comprising the grain refiner is cast prior to allowing the alloy to solidify.
  • the protective gas comprises an inert gas such as a noble gas, e.g. helium or argon. More preferably the protective gas is a mixture of argon and SF 6 .
  • the grain refiner is preferably prepared by high energy milling, which is an effective method for preparing the desired grain refiner, which has a comparatively high melting point, by solid phase reaction.
  • the grain refiner can be added to the melt of magnesium-aluminum alloy in a similar fashion to zirconium in aluminum-free magnesium alloys. Then the prepared refiner is added in the melt of magnesium alloys as nucleants.
  • the protective gas atmosphere is preferably continuously or intermittedly renewed in order to prevent oxidation of magnesium and/or aluminum during the milling process. If the protective gas atmosphere is renewed intermittedly, renewing of the atmosphere preferably takes place at least 3 times, more preferably at least 5 times during the milling process.
  • a mill ball made of zirconium oxide or high strength steel is used during the milling process in order to decrease the harmful effects caused by iron.
  • the ratio of ball to powder preferably lies between 5:1 and 10:1, more preferably between 6:1 and 8:1.
  • the milling time is preferably chosen to be between 4 hours and 8 hours, more preferably between 5 hours and 7 hours.
  • the dwell time before starting the milling process is preferably chosen to be between 1 hour and 4 hours, more preferably between 1 hour and 3 hours.
  • the materials When preparing the grain refiner by high energy milling the materials shall preferably be used in form of their powders.
  • the particle sizes of materials used to prepare the grain refiner by high energy milling is preferably between 100 ⁇ m and 400 ⁇ m, more preferably between 250 ⁇ m and 350 ⁇ m.
  • Materials used to prepare the grain refiner preferably have a purity of from 99 % to 99.999%, more preferably between 99.9% and 99.99%.
  • the grain refiner is milled to a particle sizes of between 0.1 nm and 50 nm, more preferably between 0.1 nm and 10 nm.
  • the grain refiner according to the present invention is particularly effective for cast magnesium-aluminum alloys.
  • This includes e.g. gravity-cast magnesium-aluminum based alloys, die casting magnesium-aluminum based alloys, semi solid casting magnesium-aluminum based alloys, rheocasting magnesium-aluminum based alloys and continuous casting magnesium-aluminum based alloys.
  • the temperature of the molten alloy is preferably 720°C or higher in order to avoid the segregation of the nanoparticles of the grain refiner.
  • the more elevated the temperature the shorter the time it takes to achieve the grain refinement.
  • a temperature of the melt between 720°C and 760°C is preferable, most preferably around 750°C.
  • the content of grain refiner added in cast magnesium-aluminum based alloys is preferably between 0.1 and 2% by weight, more preferably between 0.5 and 1.5% by weight. When the content of its addition is below 0.1% by weight, the effect of grain refinement may not be sufficient. When the content of its addition is higher than 2% by weight, the residual grain refiner may influence the properties of magnesium alloys.
  • the melt is preferably stirred in order to obtain homogeneously distributed alloys.
  • the stirring speeds are preferably between 150 rpm and 300 rpm, more preferably between 150 and 250 rpm.
  • the stirring time is preferably between 10 min and 60 min, more preferably between 20 min and 40 min.
  • the dwell time after the addition of grain refiner is advantageous for the grain refinement of cast magnesium-aluminum based alloys.
  • the dwell time should preferably be between 10 min and 90 min, more preferably between 30 min and 60 min.
  • a cylindrical steel pot was used to prepare the grain refiner.
  • pure argon was used to clean the atmosphere for 5 times.
  • the milling speed was 1000 rpm.
  • a zirconium oxide ball was selected, and the ratio of ball to powder was 8:1.
  • the milling time was 5-20 hours (see Table 1).
  • the dwell time between two millings was 2 hours.
  • the crucible canopy was not opened.
  • Table 1 The compositions of samples after milled for different time are listed in Table 1.
  • FIGS. 1(a)-(c) are optical microstructures showing the grain refining ability of as-received powders after they were added to magnesium-3wt.% aluminum alloy at 750 °C. It can be found that the grain size decreases with the addition of different grain refiners.
  • FIG. 2 are optical microstructures showing the grain refining efficiency of as-received powders after they were added to magnesium-3 wt.% aluminum alloy at 750°C.
  • the grain size reduces with increasing the content of grain refiners.
  • the detailed values are shown in FIG. 3 .
  • the smallest value of grain size is obtained when adding 1.5 wt.% grain refiner.
  • the smallest average grain size is 67 ⁇ m.
  • FIG 4 shows the relationship between the average grain size of magnesium-3 wt.% aluminum alloys and the milling time of Mg 0.3 Al 0.4 C 0.15 RE 0.15 grain refiner. The smallest grain size is observed in the alloy by adding the grain refiner with milling time for 20 hours.
  • compositions of powder before milling are shown in Table 2, in which the unit is "atom %”.
  • a cylindrical steel pot was used to prepare the grain refiner.
  • the pure argon was used to clean the atmosphere for 5 times.
  • the milling speed was 1000 rpm.
  • a zirconium oxide ball was selected, and the ratio of ball to powder was 8:1.
  • the milling time was 5-20 hours (see Table 2).
  • the dwell time between two milling was 2 hours.
  • the crucible canopy should not be opened.
  • Table 2 The compositions of samples after milled for different time are also listed in Table 2.
  • FIG. 1(b) The typical microstructure of magnesium-3 wt.% aluminum alloy with the addition of grain refiner Mg 0.3 Al 0.4 C 0.15 Ca 0.15 is shown in FIG. 1(b) .
  • the grain is largely refined after the addition of this refiner.
  • FIG. 5 shows the average grain size as a function of the content of grain refiner Mg 0.3 Al 0.4 C 0.15 Ca 0.15 added to magnesium-3 wt.% aluminum alloy.
  • the grain size decreases with increasing the content of refiner. After adding more than 1 wt.% refiners, the grain size tends to be stable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (9)

  1. Kornfeinungsmittel zur Verwendung in einer Magnesiumlegierung, das die folgende chemische Formel aufweist:

            Mg100-x-y-zAlxCyRz

    in der R ein Element ist, das aus der Gruppe bestehend aus Silicium, Calcium oder Strontium ausgewählt ist, x von 10 bis 50 At.%, y von 10 bis 35 At.% und z von 1 bis 20 At.% ist, mit der Maßgabe, dass x+y+z weniger als 100 At.% ist.
  2. Verfahren zur Herstellung einer Magnesiumlegierung mit feiner Körnung, bei dem eine Magnesium und Aluminium umfassende Legierung unter einer Schutzgasatmosphäre geschmolzen wird, zu der geschmolzenen Magnesium-Aluminium Legierung ein Kornfeinungsmittel gemäß Anspruch 1 zugegeben wird und die Legierung sich verfestigen gelassen wird.
  3. Verfahren nach Anspruch 2, bei dem die das Kornfeinungsmittel umfassende Magnesium-Aluminium Legierung gegossen wird, bevor die Legierung sich verfestigen gelassen wird.
  4. Verfahren nach einem der Ansprüche 2 oder 3, bei dem das Schutzgas Argon umfasst.
  5. Verfahren nach Anspruch 4, bei dem das Schutzgas weiterhin SF6 umfasst.
  6. Verfahren nach einem der Ansprüche 2 bis 5, bei dem das Kornfeinungsmittel in Form eines gemahlenen Pulvers mit einer Teilchengröße von weniger als 50 nm verwendet wird.
  7. Verfahren nach einem der Ansprüche 2 bis 6, bei dem die geschmolzene Magnesium-Aluminium Legierung zwischen 10 Minuten und 60 Minuten nach Zugabe des Kornfeinungsmittels gerührt wird.
  8. Verfahren nach einem der Ansprüche 2 bis 7, bei dem die Magnesium-Aluminium Legierung aus der Gruppe bestehend aus Magnesium-Aluminium-Zink Legierungen und Magnesium-Aluminium-Mangan Legierungen ausgewählt ist.
  9. Verfahren nach Anspruch 8, bei dem die Magnesium-Aluminium Legierung aus der Gruppe bestehend aus AM50, AM60, AM201, AZ10, AZ31, AZ63, AZ80, AZ91, AE44, AE42, AJ53, AS41 und AS42 ausgewählt ist.
EP11152825.3A 2011-02-01 2011-02-01 Legierung auf Magnesium-Aluminium-Basis mit Kornverfeiner Not-in-force EP2481822B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP11152825.3A EP2481822B1 (de) 2011-02-01 2011-02-01 Legierung auf Magnesium-Aluminium-Basis mit Kornverfeiner
ES11152825T ES2424005T3 (es) 2011-02-01 2011-02-01 Aleación basada en magnesio-aluminio con refinador de grano
US13/352,632 US20120195789A1 (en) 2011-02-01 2012-01-18 Magnesium-aluminum based alloy
CA2765465A CA2765465A1 (en) 2011-02-01 2012-01-25 Magnesium-aluminum based alloy
CN201210022182.3A CN102628133B (zh) 2011-02-01 2012-02-01 镁铝合金

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11152825.3A EP2481822B1 (de) 2011-02-01 2011-02-01 Legierung auf Magnesium-Aluminium-Basis mit Kornverfeiner

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EP2481822A1 EP2481822A1 (de) 2012-08-01
EP2481822B1 true EP2481822B1 (de) 2013-05-08

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US (1) US20120195789A1 (de)
EP (1) EP2481822B1 (de)
CN (1) CN102628133B (de)
CA (1) CA2765465A1 (de)
ES (1) ES2424005T3 (de)

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US9092928B2 (en) 2005-07-01 2015-07-28 The Invention Science Fund I, Llc Implementing group content substitution in media works
US9065979B2 (en) 2005-07-01 2015-06-23 The Invention Science Fund I, Llc Promotional placement in media works
US20070276757A1 (en) * 2005-07-01 2007-11-29 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Approval technique for media content alteration
US9230601B2 (en) 2005-07-01 2016-01-05 Invention Science Fund I, Llc Media markup system for content alteration in derivative works
US8126938B2 (en) 2005-07-01 2012-02-28 The Invention Science Fund I, Llc Group content substitution in media works
US9583141B2 (en) 2005-07-01 2017-02-28 Invention Science Fund I, Llc Implementing audio substitution options in media works
US9426387B2 (en) 2005-07-01 2016-08-23 Invention Science Fund I, Llc Image anonymization
US20070005651A1 (en) 2005-07-01 2007-01-04 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Restoring modified assets
US9215512B2 (en) 2007-04-27 2015-12-15 Invention Science Fund I, Llc Implementation of media content alteration
CN104087804B (zh) * 2014-07-28 2016-09-07 胡贤晨 一种抗蠕变镁合金及其制备方法
CN112030049A (zh) * 2020-07-14 2020-12-04 中国石油天然气股份有限公司 一种可控溶解镁合金材料及其制备方法
CN112921225B (zh) * 2021-02-16 2022-06-21 河南工学院 一种用于Mg-Al系合金的铝包覆纳米Al4C3颗粒状晶粒细化剂及其制备方法
CN115198128A (zh) * 2022-07-08 2022-10-18 宝胜（宁夏)线缆科技有限公司 高品质再生铝硅系合金零碳制造工艺

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CA1289748C (en) * 1985-03-01 1991-10-01 Abinash Banerji Producing titanium carbide
CN1151293C (zh) * 2002-11-25 2004-05-26 山东大学 一种镁合金用细化剂及其制备方法
US8016957B2 (en) * 2006-02-03 2011-09-13 GM Global Technology Operations LLC Magnesium grain-refining using titanium
CN100516262C (zh) * 2007-10-11 2009-07-22 武汉理工大学 镁及镁合金复合晶粒细化剂的制备方法
CN101774013B (zh) * 2010-02-26 2012-05-23 华南理工大学 用于Mg-Al合金的晶粒复合细化剂及其制备方法

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Publication number Publication date
US20120195789A1 (en) 2012-08-02
CN102628133B (zh) 2015-07-08
CA2765465A1 (en) 2012-08-01
EP2481822A1 (de) 2012-08-01
CN102628133A (zh) 2012-08-08
ES2424005T3 (es) 2013-09-26

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