CN101565789A - Ductile magnesium alloy - Google Patents

Ductile magnesium alloy Download PDF

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Publication number
CN101565789A
CN101565789A CNA2009101353616A CN200910135361A CN101565789A CN 101565789 A CN101565789 A CN 101565789A CN A2009101353616 A CNA2009101353616 A CN A2009101353616A CN 200910135361 A CN200910135361 A CN 200910135361A CN 101565789 A CN101565789 A CN 101565789A
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CN
China
Prior art keywords
magnesium alloy
described magnesium
respect
alloy
gross weight
Prior art date
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Pending
Application number
CNA2009101353616A
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Chinese (zh)
Inventor
卡斯滕·布拉韦特
乌尔里希·凯纳
沃尔夫冈·迪策尔
安德烈·迪策
克里斯蒂亚娜·沙夫
普雷德拉格·日瓦诺维奇
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GKSS Forshungszentrum Geesthacht GmbH
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GKSS Forshungszentrum Geesthacht GmbH
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Publication of CN101565789A publication Critical patent/CN101565789A/en
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    • 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
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent

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  • 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)

Abstract

The present invention relates to a corrosion resistant magnesium alloy which can be prepared with a justifiable expenditure of energy from scrap or impure copper containing precursors and displays a ductility such that it can be used as a casting or kneading material. The magnesium alloy contains, relative to the total weight of the magnesium alloy, 1 to 9 wt. % aluminium, 0.6 to 6 wt. % zinc, 0.1 to 2 wt. % manganese, 0 to 2 wt. % rare earth elements, 0.5 to 2 wt. % copper, wherein the weight ratio of aluminium to zinc lies in the range from 1:1 to 2:1.

Description

Ductile magnesium alloy
Technical field
The present invention relates to a kind of corrosion resistant magnesium alloy.
Background technology
If very little this alloy so of the content of copper, iron and nickel is corrosion-resistant in the known magnesium alloy.In the alloy of AZ (magnesium with aluminum and zinc), AM (magnesium with aluminium and manganese), AS (magnesium with aluminium and silicon) and AJ (magnesium with aluminium and strontium) class, the maximum content that allows mainly is set at the copper of 250ppm, the nickel of 10ppm and the iron of 50ppm.Soc.AutomotiveEngineers according to people such as Bakke, paper 1999-01-0926,1999,1-10 page or leaf and Kammer (chief editor): Magnesiumtaschenbuch, Aluminiumverlag D ü sseldorf, 2000, first version, allow content if surpass the maximum of copper, nickel and/or iron, produce remarkable corrosion so mainly due to spot corrosion.
Can utilize much smaller than the energy expenditure of primary alloy and make secondary magnesium alloy, but secondary magnesium alloy inevitably packet content be higher than maximum copper, nickel and the iron that allows content.Buy waste material by recycle, can only with very high cost just can make or at all can't manufactured copper, nickel and/or iron level be lower than the maximum magnesium alloy that allows content.Yet, by a kind of as can be known corrosion resistant secondary magnesium alloy of WO 2007/009435A1.Although copper and mickel content is higher, but the disclosed magnesium alloy of WO 2007/009435A1 shown can with the quite or better corrosion resistance nature of the primary magnesium alloy of high purity, and comprise zinc, the 0.1-2wt.% of aluminium, the 2.5-10wt.% of 10-20wt.% manganese, 0.3-2wt.% copper and/or be up to total nickel, cobalt, iron, silicon, zirconium, the beryllium of 1.5wt.%.Yet these alloys have more crisp shortcoming, and this makes them can't be used for some working method such as extruding, forging, rolling, also can't be used for coming endergonic application via viscous deformation.
Summary of the invention
Therefore, the invention provides corrosion resistant magnesium alloy, this magnesium alloy can not need very high energy expenditure to prepare by the waste material of recycle purchase and is ductile.
Can realize this purpose by following magnesium alloy: this magnesium alloy comprises with respect to its gross weight: the manganese of the aluminium of 1-9wt.%, the zinc of 0.6-6wt.%, 0.1-2wt.%, the rare earth element of 0-2wt.%, the copper of 0.5-2wt.%, wherein aluminium is 1: 1～2: 1 to the ratio of the weight percent of zinc.Can obtain preferred embodiment by dependent claims.
Unexpectedly find, though higher according to copper content in the magnesium alloy of the present invention, to compare with the primary magnesium alloy of high purity, its erosion resistance is good equally.In addition, keep ductility according to magnesium alloy of the present invention.
Be preferably 2-7.5wt.% according to the aluminium content of magnesium alloy of the present invention with respect to the gross weight of described magnesium alloy, more preferably 3-6wt.%.Be preferably 1-5wt.% according to the zinc content of magnesium alloy of the present invention with respect to the gross weight of described magnesium alloy, more preferably 2-4wt.%.Manganese content according to magnesium alloy of the present invention is preferably 0.1-1wt.%, more preferably 0.2-0.75wt.%.Copper content according to magnesium alloy of the present invention is preferably 0.5-1wt.%, more preferably 0.5-0.7wt.%.
In addition, find unexpectedly that by adding rare earth such as cerium, neodymium, yttrium, scandium, gadolinium or its mixture, erosion resistance further improves.Especially, can therefore reduce the negative impact (if nickel existence) of nickel.Total ree content is preferably with respect to the gross weight of magnesium alloy and is up to 2wt.%.
Can also comprise nickel, iron and/or silicon according to magnesium alloy of the present invention.Nickel content preferably less than 0.005wt.%, is more preferably less than 0.001wt.%, further preferably less than 0.0005wt.% with respect to the gross weight of magnesium alloy.Iron level should preferably less than 0.01wt.%, be more preferably less than 0.005wt.% less than 0.05wt.% with respect to the gross weight of magnesium alloy, and silicone content should be less than 0.1wt.%, preferably less than 0.05wt.% with respect to the gross weight of magnesium alloy.
Comprise the waste material of copper, nickel and/or iron or impure magnesium precursor by fusing, afterwards each components contents in the described alloy is set at correspondence, can be used as secondary alloy manufacturing according to magnesium alloy of the present invention according to magnesium alloy of the present invention.Can and utilize relatively little energy expenditure to make this magnesium alloy with suitable cost.
Magnesium alloy according to the present invention can be used as cast material (sandbox foundry goods, ingot foundry goods, die casting and semi-solid foundry goods) and is used for extruding, forging, rolling etc. as machinable material (kneading material).
Embodiment
Embodiment:
To illustrate in greater detail the present invention by means of following examples now.According to DIN 50021, use salt-fog test and in 3.5% sodium chloride solution, flood, compare corrosion check.In dipping is measured, determine erosion rate by the generation of measuring hydrogen.In salt-fog test, determine mass loss.
In table 1, will compare according to the erosion rate of AM 50 alloys (AMC) of magnesium alloy of the present invention (AMZC), pure zinciferous magnesium alloy (AMZ503), pure AM50 alloy and copper modification.(in wt.%) is as shown in table 2 for the content of the aluminium of the magnesium alloy of listing in the table 1, zinc, manganese, copper, nickel, iron and silicon, table 3 shows that wherein surplus is always magnesium according to alloy of the present invention, comparative alloy AMZ501, AMZ502, AMZ505 and AM50 according to WO 2007/009435A1 and the mechanical property of AZC1231.
Table 1:
Alloy Erosion rate salt-fog test (mm/) Erosion rate dipping (mm/)
AMZC 0.6 1.7
AMZ503 0.17 1.1
AM50 0.63 4.5
AMC 8.99 32.9
AZC1231 1.00 6.57
Table 2:
Alloy Al Zn Mn Cu Ni Fe Si
AMZC 5.59 3.18 0.25 0.54 0.00014 0.0013 0.026
AMZ503 5.3 3.19 0.25 0.0077 0.00021 0.0015 0.028
AM50 4.9 0.02 0.26 0.0077 0.00017 0.00068 0.026
AMC 4.84 0.023 0.26 0.52 0.000082 0.00092 0.028
AZC1231 11.7 3.04 0.48 0.47 0.0032 0.0087 0.39
Table 3:
Alloy Yield-point (MPa) Tensile strength (MPa) Tension set (%)
AMZC 73 226 10.9
AMZ501 67 214 13.2
AMZ502 65 207 10.2
AMZ505 67 193 11.2
AM50 54 199 13.2
AZC1231 152 189 0.5
Data presentation according to the erosion rate of magnesium alloy of the present invention (AMZC) can with the erosion rate of isozygoty golden AMZ503 and AM 50 quite or even improvement arranged.On the other hand, AM 50 alloys of copper modification demonstrate unacceptable erosion rate.
Without wishing to be held to theory, think microstructure according to magnesium alloy of the present invention be characterised in that secondary phase content low with β Mg mutually 17Al 12Change.With different from the known alloy of WO 2007/009435A1, inferior looks does not form network organization.This has positively effect for the ductility according to alloy of the present invention, and is as shown in table 3.Infer β by obtaining changing, and part is substituted mutually by quaternary MgAlZnCu and suppresses with zinc generation alloying.Local element former (local elementformers) copper, nickel, cobalt and iron and their intermetallic phase be strapped in this mutually in, nickel, cobalt and iron also pass through Al in addition 8Mn 5Fetter mutually, thereby they significantly reduce the negative impact of erosion resistance.On the other hand, the microstructure of pure AM 50 alloys mainly comprises β mutually as time looks, and this is secondary to promote corrosion and do not form as network by local element formation effect.Therefore, higher copper, nickel, cobalt and the iron level of alloy tolerable according to the present invention.Zinc and copper content have increased the intensity of alloy, and have no significant effect ductility (seeing Table 3), make the more anti-creep of alloy in addition.And, golden AMZ 503 or AM 50 are different with isozygotying, comprise the waste material of copper, nickel and/or iron or impure precursor by fusing, can set each component concentration of described alloy thereafter, can adopt reasonable energy consumption to make magnesium alloy according to the present invention as secondary alloy.

Claims (11)

1. magnesium alloy, gross weight with respect to described magnesium alloy comprises: the manganese of the aluminium of 1-9wt.%, the zinc of 0.6-6wt.%, 0.1-2wt.%, the rare earth element of 0-2wt.%, the copper of 0.5-2wt.%, wherein aluminium to the ratio of the weight percent of zinc in 1: 1～2: 1 scopes.
2. magnesium alloy according to claim 1 is characterized in that aluminium content is 2-7.5wt.% with respect to the gross weight of described magnesium alloy.
3. according to any described magnesium alloy in claim 1 or 2, it is characterized in that zinc content is 1-5wt.% with respect to the gross weight of described magnesium alloy.
4. according to any described magnesium alloy in the aforementioned claim, it is characterized in that manganese content is 0.1-1wt.% with respect to the gross weight of described magnesium alloy.
5. according to any described magnesium alloy in the aforementioned claim, it is characterized in that copper content is 0.5-1wt.% with respect to the gross weight of described magnesium alloy.
6. according to any described magnesium alloy in the aforementioned claim, it is characterized in that it also comprises nickel, iron and/or silicon.
7. magnesium alloy according to claim 6 is characterized in that nickel content is less than 0.005wt.% with respect to the gross weight of described magnesium alloy.
8. according to any described magnesium alloy in claim 6 or 7, it is characterized in that iron level is less than 0.01wt.% with respect to the gross weight of described magnesium alloy.
9. according to any described magnesium alloy among the claim 6-8, it is characterized in that silicone content is less than 0.1wt.% with respect to the gross weight of described magnesium alloy.
10. make method, it is characterized in that: with copper bearing precursor of impure bag or magnesium scrap melting, then according to any each component concentration of setting described alloy among the claim 1-9 according to any described magnesium alloy among the claim 1-9.
11. according to the purposes of magnesium alloy any among the claim 1-9 as casting and/or machinable material.
CNA2009101353616A 2008-04-23 2009-04-23 Ductile magnesium alloy Pending CN101565789A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008020523.0A DE102008020523B4 (en) 2008-04-23 2008-04-23 Ductile magnesium alloy
DE102008020523.0 2008-04-23

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US (1) US20090269236A1 (en)
EP (1) EP2116622B1 (en)
JP (1) JP2009263792A (en)
CN (1) CN101565789A (en)
AU (1) AU2009201545B2 (en)
CA (1) CA2662603C (en)
DE (1) DE102008020523B4 (en)
IL (1) IL198126A0 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260811A (en) * 2011-07-22 2011-11-30 曹金 Magnesium-based blocking explosion-proof alloy material
CN103397235A (en) * 2013-08-16 2013-11-20 重庆大学 Magnesium-aluminum-zinc-manganese-copper alloy and preparation method thereof
CN108884528A (en) * 2016-03-31 2018-11-23 株式会社栗本铁工所 Degradability mg alloy

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* Cited by examiner, † Cited by third party
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JP5405392B2 (en) * 2009-06-17 2014-02-05 株式会社豊田中央研究所 Recycled magnesium alloy, method for producing the same, and magnesium alloy
US8435444B2 (en) 2009-08-26 2013-05-07 Techmag Ag Magnesium alloy
JP5595891B2 (en) * 2010-12-17 2014-09-24 株式会社豊田中央研究所 Method for producing heat-resistant magnesium alloy, heat-resistant magnesium alloy casting and method for producing the same
CN104630474A (en) * 2013-11-07 2015-05-20 丹阳智盛合金有限公司 Technology for production of iron-chromium-aluminum alloy by submerged arc furnace
CN114277297B (en) * 2021-12-22 2023-04-07 重庆大学 Magnesium-based composite material with improved heat resistance and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260811A (en) * 2011-07-22 2011-11-30 曹金 Magnesium-based blocking explosion-proof alloy material
CN103397235A (en) * 2013-08-16 2013-11-20 重庆大学 Magnesium-aluminum-zinc-manganese-copper alloy and preparation method thereof
CN103397235B (en) * 2013-08-16 2015-08-12 重庆大学 A kind of magnesium-aluminum-zinc-manganese-copper alloy and preparation method thereof
CN108884528A (en) * 2016-03-31 2018-11-23 株式会社栗本铁工所 Degradability mg alloy

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DE102008020523A1 (en) 2009-10-29
AU2009201545A1 (en) 2009-11-12
EP2116622A1 (en) 2009-11-11
AU2009201545B2 (en) 2014-03-27
DE102008020523B4 (en) 2014-05-15
CA2662603A1 (en) 2009-10-23
US20090269236A1 (en) 2009-10-29
IL198126A0 (en) 2009-12-24
JP2009263792A (en) 2009-11-12
CA2662603C (en) 2016-02-09
EP2116622B1 (en) 2015-07-22

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