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WO2006000022A1 - Alliage de magnesium moule - Google Patents

Alliage de magnesium moule Download PDF

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Publication number
WO2006000022A1
WO2006000022A1 PCT/AU2005/000903 AU2005000903W WO2006000022A1 WO 2006000022 A1 WO2006000022 A1 WO 2006000022A1 AU 2005000903 W AU2005000903 W AU 2005000903W WO 2006000022 A1 WO2006000022 A1 WO 2006000022A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
alloy
magnesium
calcium
alloys
Prior art date
Application number
PCT/AU2005/000903
Other languages
English (en)
Inventor
Trevor Bruce Abbott
Original Assignee
Cast Centre 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
Priority claimed from AU2004903446A external-priority patent/AU2004903446A0/en
Application filed by Cast Centre Pty Ltd filed Critical Cast Centre Pty Ltd
Priority to US11/571,038 priority Critical patent/US20070212250A1/en
Priority to EP05752425A priority patent/EP1761652A4/fr
Priority to CA002572002A priority patent/CA2572002A1/fr
Priority to MXPA06015208A priority patent/MXPA06015208A/es
Priority to CN2005800281663A priority patent/CN101006191B/zh
Priority to AU2005256143A priority patent/AU2005256143A1/en
Priority to JP2007516892A priority patent/JP4729567B2/ja
Publication of WO2006000022A1 publication Critical patent/WO2006000022A1/fr
Priority to IL180193A priority patent/IL180193A0/en
Priority to NO20070414A priority patent/NO20070414L/no

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
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent

Definitions

  • the present invention relates to magnesium/zinc/aluminium (Mg-Zn-Al) alloys which contain small amounts of calcium and/or beryllium.
  • magnesium alloys are well recognised as commercially desirable materials.
  • the most commonly used magnesium alloy is AZ91 which contains about 90% magnesium, 9% aluminium and 1% zinc.
  • zinc is about 65% of the price of magnesium and hence magnesium alloys of increased zinc content would be desirable provided that they exhibited commercially satisfactory properties.
  • a serious disadvantage of using magnesium alloys is the danger of ignition of molten alloy. Magnesium alloys which are sufficiently resistant to oxidation to obviate the need for protective cover gases or the like when molten alloy is exposed to air would be advantageous.
  • molten magnesium burns or otherwise reverts to the oxide in very substantial part .
  • magnesium base alloys oxidise, under some conditions, to a comparatively severe extent. Since extensive handling of magnesium and magnesium base alloys in the molten condition is a necessary preliminary to operations designed to shape or work the metal, the difficulties presented by this pronounced tendency to oxidise are encountered in almost every instance and are universal in the magnesium industry.” "Confronted with these problems the industry has devised methods and devices by which to shield molten magnesium and magnesium base alloys from contact with air and moisture, or other deleterious media, during manufacturing operations. One such method is to envelop the molten metal in a protective gas.
  • US patent no. 5855697 (Luo et al) relates to a magnesium alloy having superior elevated temperature properties and is not concerned with oxidation suppression. US 5855697 notes that calcium addition is known to improve the high-temperature strength and creep resistance and that calcium contents of 0.2% by weight and greater are desirable. It is further noted that such calcium additions severely deteriorate castability rendering the alloy incapable of being cast by conventional die casting processes. US 5855697 teaches that the castability of a magnesium-aluminium-calcium alloy can be restored by inclusion of zinc.
  • the presence of zinc is said to enable calcium to "be added in amounts up to 2 weight %, preferably up to 1.5 weight %, in order for the alloy to achieve the maximum creep resistance while maintaining good die-castability.
  • US 5855697 exemplified the below listed alloys. Accordingly, US 5855697 does not exemplify an alloy containing more than 8.15% Zn.
  • the present invention provides an alloy consisting of: zinc (Zn) and aluminium (Al) in amounts which fall within a quadrangle defined by lines AB, BC, CD, and DA wherein: AA iiss 1100% Zn - 2.5% Al, B is 10 Zn - 5% Al, C is 13 Zn - 6.4% Al, and D is 19 Zn - 2.5 % Al; calcium (Ca) and/or beryllium (Be) in amounts which fall within a quadrangle defined by lines EF, FG, GH and HE wherein: E is 0.01% Ca - 0% Be, F is 1% Ca - 0% Be, G is 0% Ca - 0.0025% Be, and HH iiss 0% Ca - 0.0001% Be optionally Mn; and the balance Mg except for incidental impurities.
  • All alloys of the present invention contain a minimum of 10% zinc, preferably greater than 11% zinc, more preferably greater than 12% zinc, more preferably about 12-14% zinc, and most preferably about 12-13% zinc. Most surprisingly, the present inventor has ascertained that such zinc additions suppress the ignition of the alloy in the molten state in the absence of alkaline earth elements such as beryllium or calcium.
  • the ignition suppression is believed to be a consequence of the vapour pressures of magnesium and zinc and the amount of zinc present in the alloys.
  • the vapour pressures of zinc and magnesium above a molten alloy can be calculated using information from a paper entitled "Vapour Composition and Activities in Mg-Zn Liquid Alloy at 923K" by K.T. Jacob, S. Srikanth and Y. Waseda in Thermochimica Acta, 1988, vol 130, pages 193- 203.
  • the ratio of the vapour pressure of zinc relative to the vapour pressure of magnesium increases rapidly as the amount of zinc in the molten alloy is increased.
  • a molten alloy containing 10% by weight of zinc and 90% by weight of magnesium is calculated to produce a vapour containing 22% by weight of zinc and 78% by weight of magnesium.
  • the zinc vapour is believed to interfere with ignition of the magnesium vapour.
  • ⁇ molten alloys containing more than 10% zinc resist ignition they tend to form a blackened layer on the surface of a solidified sample.
  • the addition of a small amount of calcium and/or a small amount of beryllium has been found sufficient to result in a shiny surface appearance when solidified.
  • As little as 0.01% calcium or as little as 0.0001% beryllium have been found sufficient in combination with zinc and aluminium contents in accordance with the present invention to produce this effect.
  • the shiny surface appearance is believed to be a consequence of an enrichment in the calcium and/or beryllium content of the oxide layer formed on the surface of the melt .
  • the calcium content is preferably 0.01 - 0.5%, more preferably 0.01 - 0.3%, more preferably 0.02 - 0.3%, more preferably 0.05 - 0.3%, more preferably 0.05 - 0.2%, more preferably 0.05 - 0.15%, most preferably about 0.1%. Calcium contents in excess of 1% are undesirable because they have been found to diminish the mechanical properties of the alloys and cause die soldering when die cast .
  • the beryllium content is preferably 0.0002 - 0.0025%, more preferably 0.0002 - 0.002%, more preferably 0.0005 - 0.002%, more preferably 0.0005 - 0.0015%, more preferably 0.0005 - 0.001%, most preferably about 0.0008%.
  • Beryllium contents in excess of 0.0025% are unnecessary in order to obtain the desired effect .
  • Manganese (Mn) is an optional component of the alloys which may be included if there is a requirement for iron (Fe) removal.
  • Mn When Mn is a component it is preferably present in amounts less than 1%, more preferably less than 0.75%, more preferably 0.1 - 0.5%, more preferably 0.2 - 0.4% and most preferably about 0.3%.
  • Other elements may also form optional components of the alloys provided that they do not adversely affect commercially significant properties of the alloys .
  • the presence of iron reduces corrosion resistance.
  • alloys of the present invention contain less than 100 ppm iron, more preferably less than 40 ppm iron, and most preferably substantially no iron. The present inventor has ascertained that corrosion resistance decreases with decreasing aluminium content. All alloys of the present invention contain a minimum of 2.5% aluminium.
  • alloys of the present invention contain 2.5 - 5% aluminium, more preferably about 3 - 4.5% aluminium, and most preferably about 3.5 - 4% aluminium.
  • the present inventor has also ascertained that brittleness increases to the aluminium rich and zinc rich side of line CD.
  • the presence of nickel (Ni) reduces corrosion resistance.
  • alloys of the present invention contain less than 25 ppm nickel, more preferably less than 10 ppm nickel, and most preferably substantially no nickel .
  • the presence of silicon (Si) reduces corrosion resistance and mechanical properties.
  • alloys of the present invention contain less than 0.1% silicon, more preferably less than 0.08% silicon, and most preferably substantially no silicon.
  • various preferred embodiments of the present invention exhibit one or more other commercially desirable properties such as recyclability, castability, resistance to hot cracking, corrosion resistance, creep resistance, low sound dampening coefficients and good surface finish.
  • a significant commercial impediment to the use of magnesium alloys is the waste which results from the difficulty of recycling so-called "returns" which include runners, biscuits etc from die casting.
  • returns which include runners, biscuits etc from die casting.
  • 30 - 70% of a diecasting consists of runners and biscuits that need to be recycled. Difficulties in the recycling of magnesium alloys are generally attributed to a significant amount of surface oxides which result in high melt losses in the form of dross and sludge.
  • Table 1 lists the behaviour observed for a range of different alloys.
  • the addition of more than 10% of zinc was sufficient to prevent burning and resulted in a blackened surface.
  • Calcium additions without zinc produced a shiny surface, but 0.8% calcium was required to prevent ignition.
  • the addition of calcium to alloys with sufficient zinc to prevent burning converted the surface to a shiny appearance with as little as 0.05% calcium producing a partially shiny surface.
  • Increases in the calcium content lead to a progressive decrease in the amount of blackening. At 0.4% calcium no blackening was observed.
  • the alloys containing 10% zinc (see Table 1) turned black then ignited, while alloys with higher zinc contents did not ignite.
  • the alloys were deliberately poured at high temperature (700°C) to remove low temperature as a possible reason for absence of ignition.
  • Figures 10 and 11 illustrate the behaviour of Mg- 15%Zn and Mg-20%Zn alloys respectively. In both cases it was relatively easy to expose shiny metal which took several seconds to re-oxidize. Neither formed "cauliflower-like" growths.
  • a further series of alloys was produced all containing 0.1% calcium and varying amounts of zinc.
  • Figures 12, 13 and 14 show the appearance of the alloys immediately after pouring ( Figures 12a, 13a and 14a) then a short time (about 1 minute) later ( Figures 12b, 13b and 14b) .
  • Figures 12a and 12b show the behaviour of a zinc free alloy.
  • Figures 13a and 13b show the behaviour of an alloy containing 5% zinc. This alloy also developed “cauliflower-like” growths and ignited, but at a slower rate than the zinc free alloy of Figure 12.
  • Figures 14a and 14b show the behaviour of a 10% zinc alloy. In this alloy both the "cauliflower-like” growths and ignition were suppressed. The ultimate appearance after the sample was allowed to air cool to room temperature was unchanged from Figure 14b.
  • Example 3 Additional melts were prepared and poured into a mould in the same manner as described above in Example 1.
  • the melts contained 13% zinc, 3.6% aluminium and varying amounts of beryllium and calcium.
  • the calcium and beryllium contents of these alloys are given in Table 2.
  • Alloys 1 and 6 were calcium-free and alloys 1 - 4 were beryllium-free.
  • the final appearance of the castings is shown in Figure 15. All of the alloys that contained some calcium or beryllium solidified with a shiny skin. Alloy 1 which was free of both calcium and beryllium solidified with a blackened skin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Materials For Medical Uses (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Forging (AREA)
  • Dental Preparations (AREA)

Abstract

L'invention porte sur un alliage de magnésium contenant du zinc, de l'aluminium, du calcium et/ou du béryllium, facultativement du manganèse, le reste étant constitué de magnésium, à l'exception d'impuretés accidentelles. La teneur en zinc et en aluminium est comprise dans un quadrilatère défini par les lignes AB, BC, CD et DA et la teneur en calcium et en béryllium est comprise dans un quadrilatère défini par les lignes EF, FG, GH et HE où: A représente 10 % Zn 2,5 % Al, B représente 10 % Zn - 5 % Al, C représente 13 % Zn 6,4 % Al, D représente 19 % Zn 2,5 % Al, E représente 0,01 % Ca - 0 % Be, F représente 1 % Ca - 0 % Be, G représente 0 % Ca 0,0025 % Be, et H représente 0 % Ca 0,0001 % Be.
PCT/AU2005/000903 2004-06-24 2005-06-23 Alliage de magnesium moule WO2006000022A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US11/571,038 US20070212250A1 (en) 2004-06-24 2005-06-23 Die cast magnesium alloy
EP05752425A EP1761652A4 (fr) 2004-06-24 2005-06-23 Alliage de magnesium moule
CA002572002A CA2572002A1 (fr) 2004-06-24 2005-06-23 Alliage de magnesium moule
MXPA06015208A MXPA06015208A (es) 2004-06-24 2005-06-23 Mezcla de magnesio fundida a presion.
CN2005800281663A CN101006191B (zh) 2004-06-24 2005-06-23 模铸镁合金
AU2005256143A AU2005256143A1 (en) 2004-06-24 2005-06-23 Die cast magnesium alloy
JP2007516892A JP4729567B2 (ja) 2004-06-24 2005-06-23 ダイカストマグネシウム合金
IL180193A IL180193A0 (en) 2004-06-24 2006-12-19 Die cast magnesium alloy
NO20070414A NO20070414L (no) 2004-06-24 2007-01-24 Magnesium stopelegering.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AU2004903446A AU2004903446A0 (en) 2004-06-24 Die cast magnesium alloy
AU2004903446 2004-06-24
AU2004906768 2004-11-25
AU2004906768A AU2004906768A0 (en) 2004-11-25 Die cast magnesium alloy

Publications (1)

Publication Number Publication Date
WO2006000022A1 true WO2006000022A1 (fr) 2006-01-05

Family

ID=35781499

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2005/000903 WO2006000022A1 (fr) 2004-06-24 2005-06-23 Alliage de magnesium moule

Country Status (12)

Country Link
US (1) US20070212250A1 (fr)
EP (1) EP1761652A4 (fr)
JP (1) JP4729567B2 (fr)
KR (1) KR20070049114A (fr)
CN (1) CN101006191B (fr)
CA (1) CA2572002A1 (fr)
IL (1) IL180193A0 (fr)
MX (1) MXPA06015208A (fr)
NO (1) NO20070414L (fr)
RU (1) RU2007101661A (fr)
TW (1) TW200600588A (fr)
WO (1) WO2006000022A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2361946C1 (ru) * 2008-02-28 2009-07-20 Юлия Алексеевна Щепочкина Сплав на основе магния
EP2295613A1 (fr) * 2008-06-03 2011-03-16 National Institute for Materials Science ALLIAGE À BASE DE Mg

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102108466B (zh) * 2009-12-23 2012-07-11 中国科学院金属研究所 耐蚀的镁合金
RU2506337C1 (ru) * 2012-11-13 2014-02-10 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Литейный магниевый сплав
CN102965556B (zh) * 2012-11-20 2014-12-31 南通大学 多元Mg-Zn-Al基镁合金及其制备方法
CN104264022B (zh) * 2014-10-01 2016-08-10 无棣向上机械设计服务有限公司 一种镁合金及其制备方法
CN105132769B (zh) * 2015-09-11 2017-07-28 湖南大学 一种低铝低钙、高Ca/Al比Mg‑Ca‑Al合金及制备方法
CN105401032B (zh) * 2015-12-14 2017-08-25 宝山钢铁股份有限公司 一种低成本高导热压铸镁合金及其制造方法
CN105937005B (zh) * 2016-06-17 2019-12-06 东北大学秦皇岛分校 均匀分布粒状准晶和棒状相的时效强化镁合金及制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659377A (en) * 1979-05-23 1987-04-21 Nl Industries, Inc. Method for producing an oxidation resistant magnesium alloy melt
JPH06306523A (ja) * 1993-04-20 1994-11-01 Ube Ind Ltd 耐熱マグネシウム合金
JPH0881728A (ja) * 1994-07-12 1996-03-26 Ube Ind Ltd 耐クリープ性、耐食性を有するマグネシウム合金
US5855697A (en) * 1997-05-21 1999-01-05 Imra America, Inc. Magnesium alloy having superior elevated-temperature properties and die castability
JP2002266044A (ja) * 2001-03-09 2002-09-18 Aisin Takaoka Ltd マグネシウム合金
WO2003072840A1 (fr) * 2002-02-20 2003-09-04 Jsc 'avisma Titanium-Magnesium Works' Alliage a base de magnesium

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380200A (en) * 1942-07-10 1945-07-10 Aluminum Co Of America Magnesium base alloy
US3892565A (en) * 1973-10-01 1975-07-01 Nl Industries Inc Magnesium alloy for die casting
JP2001247926A (ja) * 2000-03-03 2001-09-14 Japan Steel Works Ltd:The 流動性に優れたマグネシウム合金およびマグネシウム合金材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659377A (en) * 1979-05-23 1987-04-21 Nl Industries, Inc. Method for producing an oxidation resistant magnesium alloy melt
JPH06306523A (ja) * 1993-04-20 1994-11-01 Ube Ind Ltd 耐熱マグネシウム合金
JPH0881728A (ja) * 1994-07-12 1996-03-26 Ube Ind Ltd 耐クリープ性、耐食性を有するマグネシウム合金
US5855697A (en) * 1997-05-21 1999-01-05 Imra America, Inc. Magnesium alloy having superior elevated-temperature properties and die castability
JP2002266044A (ja) * 2001-03-09 2002-09-18 Aisin Takaoka Ltd マグネシウム合金
WO2003072840A1 (fr) * 2002-02-20 2003-09-04 Jsc 'avisma Titanium-Magnesium Works' Alliage a base de magnesium

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200303, Derwent World Patents Index; Class M26, AN 2003-033655, XP008136053 *
DATABASE WPI Week 200362, Derwent World Patents Index; Class M26, AN 2003-663953, XP008137741 *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 02 1 November 1994 (1994-11-01) *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 07 26 March 1996 (1996-03-26) *
See also references of EP1761652A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2361946C1 (ru) * 2008-02-28 2009-07-20 Юлия Алексеевна Щепочкина Сплав на основе магния
EP2295613A1 (fr) * 2008-06-03 2011-03-16 National Institute for Materials Science ALLIAGE À BASE DE Mg
EP2295613A4 (fr) * 2008-06-03 2013-07-24 Nat Inst For Materials Science ALLIAGE À BASE DE Mg

Also Published As

Publication number Publication date
US20070212250A1 (en) 2007-09-13
CN101006191B (zh) 2010-11-24
JP4729567B2 (ja) 2011-07-20
KR20070049114A (ko) 2007-05-10
EP1761652A4 (fr) 2009-02-18
JP2008503651A (ja) 2008-02-07
RU2007101661A (ru) 2008-07-27
NO20070414L (no) 2007-03-20
CN101006191A (zh) 2007-07-25
EP1761652A1 (fr) 2007-03-14
TW200600588A (en) 2006-01-01
MXPA06015208A (es) 2007-03-15
CA2572002A1 (fr) 2006-01-05
IL180193A0 (en) 2007-06-03

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