EP1073774A1 - Production d'un alliage a base de magnesium - Google Patents

Production d'un alliage a base de magnesium

Info

Publication number
EP1073774A1
EP1073774A1 EP99910034A EP99910034A EP1073774A1 EP 1073774 A1 EP1073774 A1 EP 1073774A1 EP 99910034 A EP99910034 A EP 99910034A EP 99910034 A EP99910034 A EP 99910034A EP 1073774 A1 EP1073774 A1 EP 1073774A1
Authority
EP
European Patent Office
Prior art keywords
alloy
master alloy
alloying
molten
master
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.)
Withdrawn
Application number
EP99910034A
Other languages
German (de)
English (en)
Other versions
EP1073774A4 (fr
Inventor
Nigel Jeffrie Ricketts
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.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Australian Magnesium Operations Pty Ltd
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
Australian Magnesium Corp Pty Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Commonwealth Scientific and Industrial Research Organization CSIRO, Australian Magnesium Corp Pty Ltd filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Publication of EP1073774A1 publication Critical patent/EP1073774A1/fr
Publication of EP1073774A4 publication Critical patent/EP1073774A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent

Definitions

  • the present invention relates to a method for producing an alloy containing magnesium (Mg) and aluminium (Al) and to alloys produced by the method. It is to be understood that the alloy may contain constituents other than Mg and Al (for example, zinc
  • the present invention also relates to a master alloy suitable for use in the method for producing Mg-Al alloy.
  • Mn manganese
  • Fe iron
  • MnCl 2 manganese chloride
  • MnCl 2 reacts with molten Mg to form magnesium chloride (MgCl 2 ) which precipitates and thereby effects loss of Mg and also results in the formation of gaseous hydrochloric acid (HC1) when MnCl 2 or MgCl 2 hydrolyse in the presence of atmospheric moisture.
  • HC1 gaseous hydrochloric acid
  • US patent no. 5248477 (issued 28 September 1993) teaches a process for producing Mg-Al alloy in which Mn is added to molten Mg or molten Mg alloy as molten elemental Mn or a molten mixture of elemental Mn and Al . The process is thus a liquid-liquid alloying technique.
  • US patent no. 5248477 (issued 28 September 1993) teaches a process for producing Mg-Al alloy in which Mn is added to molten Mg or molten Mg alloy as molten elemental Mn or a molten mixture of elemental Mn and Al . The process is thus a liquid-liquid alloying technique.
  • Mn can be added as elemental Mn or it can be added in the form of a commercially available mixture of metals in particulate or powder form, usually in the form of a briquette, comprising about 75% Mn and about 25% Al " (see - 2 - column 3 lines 10-14) but teaches that "the addition of the elemental Mn in solid form has little effect on the reduction of Fe content in the melt” (see column 3 lines 18-20) .
  • US patent no. 5248477 goes on to teach that the "reason for the addition of the MnCl 2 as opposed to the addition of elemental Mn either in pure or mixed form is that the effectiveness for Fe precipitation is significantly greater and the Mn alloying efficiency itself is significantly greater as well.
  • the present invention provides a method for producing an Mg-Al alloy in an alloying vessel containing molten Mg or molten Mg alloy, the method including the steps of establishing the temperature of the molten Mg or Mg alloy in the range of 650-750°C and thereafter adding a solid master alloy containing Al and Mn to the alloying vessel whereby Mn is released for reaction with Fe in the alloying vessel.
  • the present invention provides Mg-Al alloy prepared by a method according to the first aspect of the present invention.
  • the Al-Mn master alloy is added to molten Mg or molten Mg alloy at temperature in the range 650-750°C.
  • the temperature is in the range 650-710°, more preferably 680-700°C.
  • Some of the Al alloying component and possibly other alloying components can be added to the alloying vessel separately from the Al-Mn master alloy.
  • all alloying components are - 3 - added to the alloying vessel by way of the Al-Mn master alloy.
  • the Mg-Al alloy may be produced by adding the master alloy to molten primary Mg and, where that is the case, the primary Mg may have been produced by electrolysis of anhydrous MgCl in an electrolytic cell. Molten Mg typically leaves the electrolytic cell at a temperature of about 655°C.
  • the Mg-Al alloy may be produced by adding the master alloy to molten Mg or Mg alloy derived from recycling of scrap material.
  • the conventional process where MnCl 2 is used requires heating the Mg or Mg alloy to 730-750°C, adding Al and any other alloying components (for example, Zn) over a period of 5-10 minutes, stirring in MnCl 2 over a period of about 20 minutes, and cooling the contents of the alloying vessel to about 670°C over a period of about 20 minutes prior to transferring the resulting Mg-Al alloy to a settling furnace.
  • Al and any other alloying components for example, Zn
  • the batch time for producing Mg-Al alloy in accordance with the first aspect of the present invention can be reduced as compared with the conventional MnCl 2 process because the alloying vessel does not need to be heated to 730-750°C, the Al and Mn can be added in a single step, and less time is required for cooling.
  • Reduction of batch time in accordance with the present invention is desirable in a Mg smelter because energy consumption is reduced and capital costs associated with requirement for a plurality of alloying vessels can be reduced. It is also to be noted that in contrast to the liquid-liquid alloying technique of US patent no. 5248477, the requirement for a separate vessel for melting the alloying components and the energy consumption associated therewith are avoided.
  • the present invention is also believed to be advantageous in relation to the chemical composition of Fe-Mn intermetallic compound that is formed. Without wishing to be bound by theory, it is believed that Fe-Mn intermetallic compounds formed at higher temperatures - 4 - contain a greater proportion of Fe than those formed at lower temperatures and that corrosion problems are lessened in Mg-Al alloys in which the Fe-Mn intermetallic compounds formed during their production contain lesser proportions of Fe .
  • the Al-Mn master alloy used in the process according to the first aspect of the present invention must be capable of releasing Mn for reaction with Fe when added to the Mg or Mg alloy at a temperature in the range of 650-750°C. Any Al-Mn master alloy that meets this requirement falls within the scope of the present invention but various properties of the master alloy are preferred.
  • the Al-Mn master alloy may include other alloying components, for example, Zn .
  • the master alloy contains a minority of Mn, for example, less than 10 percent by weight Mn. This is to be contrasted with the Mn-Al briquette referred to in US patent no. 5248477 which contained about 75 percent Mn .
  • the majority of the Mn in the Al-Mn master alloy is present in the form of an Al-Mn intermetallic compound (for example, AlgMn) with a minority of the Mn present as elemental Mn .
  • the Al-Mn intermetallic compound is preferably in the form of fine needles or thin platelets.
  • the balance of the Al in the master alloy is preferably ⁇ -Al .
  • the solid master alloy is added to molten Mg or Mg alloy at temperature in the range of 650- 710°C which is cooler than in prior art techniques.
  • preferred AlgMn containing solid master alloys are believed to enable lower Mg temperatures to be used because:
  • AlgMn is much more soluble in Mg than elemental Mn
  • AlgMn is surrounded by ⁇ -Al when formed with the result that the surface of AlgMn particles are not coated with an oxide - 5 - layer which would inhibit dissolution in Mg, and (3) AlgMn melts at about 705°C compared to elemental Mn which melts at 1246°C.
  • the Al-Mn master alloy has a nickel (Ni) content less than 30ppm and a copper (Cu) content less than 50ppm.
  • the master alloy is produced by cooling a molten master alloy precursor, for example, by quench casting.
  • the Al-Mn master alloy may be of granular form.
  • Granules of the Al-Mn master alloy may be produced using a water-cooled wheel in a manner analogous to that used for producing aluminium granules.
  • the use of granular Al-Mn master alloy enables the master alloy to be added to the alloying vessel from an overhead hopper under gravity.
  • the hopper is mounted on load cells or the like and has a gate enabling a predetermined mass of Al-Mn master alloy to be added to the alloying vessel.
  • the hopper is heated to drive any moisture off granular Al-Mn master alloy which obviates any requirement for an alloying pre-heat furnace.
  • the master alloy may be in the form of cast ingots in which case the master alloy is preferably added to the alloying vessel from an overhead conveyor.
  • the conveyor is preferably arranged to be heated to drive moisture from the master alloy and the ingots are preferably of a consistent mass whereby the mass of master alloy added to the alloying vessel is controllable by addition of a predetermined number of the ingots.
  • the present invention provides an Al-Mn master alloy containing less than 10% by weight Mn, wherein a majority of the Mn is in the form of an Al-Mn intermetallic compound and a minority of the Mn is elemental Mn.
  • the master alloy is suitable for use as - 6 - the master alloy in the process according to the first aspect of the present invention.
  • Example 1 Preparation of Solid Al-Mn Master Alloy Solid master alloy was prepared in two stages. In the first stage master alloy precursor was prepared by addition of a source of Mn to molten Al at 800°C to produce Al-Mn alloy containing 5.5% by weight Mn . Three sources of Mn were used, namely (a) Mn-Al splatter containing 60% by weight Mn, (b) Mn-Al Altabs containing 75% by weight Mn, and (c) Mn coarse injection powder. In all cases the master alloy precursor was prepared within 10 minutes of addition of the source of Mn by moderate stirring.
  • Mg-Al alloys were prepared by addition of solid Al-Mn master alloys from Example 1 to molten primary Mg at 680°C and 700°C. Only 5-10 minutes was required to achieve the ASTM minimum Mn level of 0.26% in the AM60 alloy at both 680°C and 700°C. After two hours of settling and a reduction in temperature of the melt to 660 °C, the Fe level was reduced from approximately 300ppm to less than 40ppm and Mn recovery was greater than 80%. - 7 -
  • Comparative Example 1 Preparation of Mg-Al Alloy Example 2 was repeated using Mn-Al splatter containing 60% by weight Mn in lieu of solid Al-Mn master alloys from Example 1. Mn from the Mn-Al splatter could not be readily released into the primary Mg at temperatures below 710°C. Even at 730°C with 20 minutes of stirring, a Mn level of only 0.20% was achieved at a Mn recovery of less than 50%. Comparative Example 2 - Preparation of Mq-Al Alloy
  • Example 2 was repeated using Mn-Al Altabs containing 75% by weight Mn in lieu of solid Al-Mn master alloys from Example 1. Mn from the Mn-Al Altabs could not be readily released into the primary Mg at temperatures below 710°C. Stirring for 20 minutes at 730°C was required to achieve the ASTM minimum Mn level with a Mn recovery of less than 80%.

Landscapes

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

Abstract

L'invention se rapporte à un procédé de production d'un alliage de magnésium et d'aluminium dans une cuve de production d'alliage contenant du magnésium en fusion ou un alliage de magnésium en fusion. Ledit procédé consiste à stabiliser la température du magnésium en fusion ou de l'alliage de magnésium en fusion dans un domaine de température compris entre 650 et 750 °C, puis à ajouter un alliage-mère solide contenant de l'aluminium et du manganèse dans la cuve de production de l'alliage où le manganèse est libéré de manière à réagir avec le fer.
EP99910034A 1998-03-20 1999-03-22 Production d'un alliage a base de magnesium Withdrawn EP1073774A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPP2469A AUPP246998A0 (en) 1998-03-20 1998-03-20 Magnesium alloying
AUPP246998 1998-03-20
PCT/AU1999/000189 WO1999049089A1 (fr) 1998-03-20 1999-03-22 Production d'un alliage a base de magnesium

Publications (2)

Publication Number Publication Date
EP1073774A1 true EP1073774A1 (fr) 2001-02-07
EP1073774A4 EP1073774A4 (fr) 2002-01-23

Family

ID=3806731

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99910034A Withdrawn EP1073774A4 (fr) 1998-03-20 1999-03-22 Production d'un alliage a base de magnesium

Country Status (9)

Country Link
EP (1) EP1073774A4 (fr)
AU (1) AUPP246998A0 (fr)
CA (1) CA2324961A1 (fr)
CZ (1) CZ20003374A3 (fr)
IL (1) IL138526A0 (fr)
IS (1) IS5630A (fr)
MX (1) MXPA00009225A (fr)
NO (1) NO20004676L (fr)
WO (1) WO1999049089A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2215056C2 (ru) * 2001-12-26 2003-10-27 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Сплав на основе магния и способ его получения
RU2218438C2 (ru) * 2001-12-26 2003-12-10 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Сплав на основе магния и способ его получения

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179287A (en) * 1978-12-19 1979-12-18 Union Carbide Corporation Method for adding manganese to a molten magnesium bath
JPH0849025A (ja) * 1994-08-05 1996-02-20 Mitsui Mining & Smelting Co Ltd アルミニウム含有マグネシウム基合金製造用Ａｌ−Ｍｎ母合金添加剤

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR771023A (fr) * 1933-06-20 1934-09-28 Procédé de fabrication d'alliages de magnésium et alliages en résultant
DE700517C (de) * 1937-04-16 1940-12-21 Georg Von Giesche S Erben Verguetbare Magnesiumlegierung
GB533266A (en) * 1939-04-27 1941-02-10 Fritz Christen Improvements in and relating to magnesium alloys
GB628289A (en) * 1946-05-02 1949-08-25 Bendix Aviat Corp Improvements in or relating to the heat treatment of magnesium alloy castings
US5248477A (en) * 1991-09-12 1993-09-28 The Dow Chemical Company Methods for producing high purity magnesium alloys

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179287A (en) * 1978-12-19 1979-12-18 Union Carbide Corporation Method for adding manganese to a molten magnesium bath
JPH0849025A (ja) * 1994-08-05 1996-02-20 Mitsui Mining & Smelting Co Ltd アルミニウム含有マグネシウム基合金製造用Ａｌ−Ｍｎ母合金添加剤

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
EDITOR-IN-CHIEF THADDEUS B. MASSALSKI: "Binary Alloy Phase Diagrams" December 1990 (1990-12) , WILLIAM W. SCOTT, JR. , USA XP002182507 volume 1 * page 172 - page 173 * *
I. J. POLMEAR: "Light Alloys, Metallurgy of the light metals" 1995 , ARNOLD , GB, LONDON XP002182508 * page 206 * *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 06, 28 June 1996 (1996-06-28) & JP 08 049025 A (MITSUI MINING & SMELTING CO LTD), 20 February 1996 (1996-02-20) *
See also references of WO9949089A1 *

Also Published As

Publication number Publication date
NO20004676D0 (no) 2000-09-19
EP1073774A4 (fr) 2002-01-23
MXPA00009225A (es) 2002-06-04
IL138526A0 (en) 2001-10-31
WO1999049089A1 (fr) 1999-09-30
NO20004676L (no) 2000-11-09
CZ20003374A3 (cs) 2001-11-14
IS5630A (is) 2000-09-19
CA2324961A1 (fr) 1999-09-30
AUPP246998A0 (en) 1998-04-09

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