EP2074236A2 - Magnesium-gadolinium-legierungen - Google Patents

Magnesium-gadolinium-legierungen

Info

Publication number
EP2074236A2
EP2074236A2 EP07804280A EP07804280A EP2074236A2 EP 2074236 A2 EP2074236 A2 EP 2074236A2 EP 07804280 A EP07804280 A EP 07804280A EP 07804280 A EP07804280 A EP 07804280A EP 2074236 A2 EP2074236 A2 EP 2074236A2
Authority
EP
European Patent Office
Prior art keywords
alloy
amount
present
zinc
yttrium
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.)
Granted
Application number
EP07804280A
Other languages
English (en)
French (fr)
Other versions
EP2074236B1 (de
Inventor
Timothy E. Wilks
Sarka Jeremic
Phillip David Rogers
Paul Lyon
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.)
Magnesium Elektron Ltd
Original Assignee
Magnesium Elektron 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 Magnesium Elektron Ltd filed Critical Magnesium Elektron Ltd
Publication of EP2074236A2 publication Critical patent/EP2074236A2/de
Application granted granted Critical
Publication of EP2074236B1 publication Critical patent/EP2074236B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent

Definitions

  • This invention relates to gadolinium-containing magnesium alloys, particularly those which possess high strength combined with corrosion resistance, and an optimised balance of strength and ductility.
  • the described alloys also have exceptional high temperature performance for magnesium alloys.
  • the alloys of the present invention have been developed as extrusion alloys, but can be rolled to produce sheets and are also suitable for forging and machining. Although they can be cast successfully to form billets, these alloys are not as suitable to use as shape casting alloys in processes such as die casting or sand casting as other magnesium alloys due to a tendency to form cracks.
  • the Russian patent SU1010880 teaches about magnesium alloys containing yttrium and gadolinium, optionally with zirconium.
  • the two specific alloys discussed in the patent specification have the mechanical properties summarised in Table 2.
  • Alloy Composition Yield Stress UTS Elongation (MPa) (MPa) (%)- 6% Y, 8-10% Gd, 0.3-1. 0% Mn 378-390 393-442 4.4-9.8- 6. 5% Y, 3. 5-5.5% Gd, 0.15-0.7% Zr 353-387 397-436 4.0-6.0
  • the Japanese patent JP10147830 teaches that an alloy containing l- ⁇ 6 wt% Gd and 6-12 wt% Y produces good strength at high temperature. Zirconium in an amount of up to 2 wt% can also be present.
  • JP9263871 also discusses the addition of Ca and other lanthanides, but we have found that the addition of Ca and certain lanthanides is very deleterious to these types of alloys.
  • the Chinese patent CN1676646 purports to teach that a broad range of alloys containing 1-6 wt% Y, 6-15wt% Gd, 0.35-0.8 wt% Zr and 0-1.5 wt% Ca can be extruded to produce extrudates of good strength, but there is little specific description of the alloys of the Examples and no clear demonstration of the utility of the described alloys near the limits of the claimed range.
  • the alloys of the present invention will generally have corrosion rates of less than 100 mils per year (mpy) in the industry standard ASTM B117 salt -fog test, and preferably less than 50 mpy. Since the above prior art does not mention the corrosion performance of the described alloys and so it can be assumed that this feature of the described alloys was in line with conventional alloys, i.e. inferior to that of the alloys of the present invention and greater than a corrosion rate of 50 mpy.
  • the amount of zinc is such that the ratio of the weight of zinc to the weight of zirconium is preferably less than 2:1, and more preferably less than 0.75:1,
  • lanthanides viz. lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and ytterbium, in an aggregate amount of less than at 0.2 at%, and preferably less than 0.1 at%,
  • the balance being magnesium, with any other element being present in an amount of no more than 0.2 at%, preferably no more than 0.1 at%, and more preferably being present only as an incidental impurity.
  • soluble heavy lanthanides are defined as elements with atomic numbers 65 to 69 inclusive and 71.
  • Soluble heavy lanthanides are those which display substantial solid solubility in magnesium. They are terbium, dysprosium, holmium, erbium, thulium and lutetium. These elements are characterised by all of them having the same hexagonal close packed metallic structure as possessed by yttrium and magnesium, and by having a metallic radius of between 0.178nm and 0.173nm. They also exist only in a trivalent state when oxidised, which thus distinguishes them from elements such as europium and ytterbium which show both tri- and bivalency and do not show any appreciable solid solubility in magnesium. When present the aggregate level of soluble heavy lanthanides should be greater than 0.1 at% in order ot contribute significantly to the mechanical properties of the alloy.
  • a particularly preferred soluble heavy lanthanide is erbium.
  • the ratio is between 1.25:1 and 1.75:1 for alloys which contain from 2.3 to 4.6 at% in total of gadolinium and at least one of soluble heavy lanthanide or yttrium. Outside this range either the strength and/or the ductility of the alloys declines. This decline becomes noticeable when the total amount of gadolinium, soluble heavy lanthanide and yttrium is below 2.0 at% and above 5.0 at%.
  • a grain refining element can be added in an amount up to its solid solubility limit in the alloy.
  • a preferred such element is zirconium. This can be added with increasing amounts generally improving the alloy's yield stress and elongation-to-failure properties. For such an effect at least 0.03 atomic per cent of zirconium should be present, and the maximum amount is the solid solubility limit of Zr in the alloy which is generally at about 0.3 atomic percent . However with both high and low levels of zirconium corrosion resistance may decline.
  • the most preferred composition for a zirconium containing alloy of the present invention is 5.5 to 6.5 wt% Y, 6.5 to 7.5 wt% Gd and 0.2 to 0.4 wt% Zr, with the remainder being magnesium and incidental impurities.
  • the level of zirconium should be from 0.3 to below 0.35% by weight in order to pass the 50 mpy salt-fog test. It has been found that the presence of small amounts of zinc are beneficial to the corrosion performance of the alloys of the present invention, but that as the level of zinc is increased the alloy's corrosion performance deteriorates.
  • the level of zinc should be from 0.07 to below 0.5at%.
  • the ratio of zinc to zirconium should not exceed 2:1, and should be preferably less than 0.75:1.
  • Any lanthanide other than the required soluble heavy lanthanide or yttrium should be present in a total amount of less than 0.2 atomic per cent, and preferably below 0.1 at%, otherwise there is interference with the formation of the desired at least one indeterminate ternary phase as described above.
  • any other element should be present in an amount of no more than 0.2 at%, preferably no more than 0.1 at%, and more preferably be present only at an incidental impurity level .
  • the alloys of the present invention may be used for extrusions, sheet, plate and forgings . Additionally they may be used for parts machined and/or manufactured from extrusions, sheet, plate or forgings .
  • a magnesium alloy DF8791 was produced containing 3.04 at % in total of yttrium and gadolinium, where the yttrium to gadolinium ratio was 1.52:1. Additionally it contained 0.15 at% zirconium, with other elements being at impurity levels.
  • Another magnesium alloy, DF8961 was produced containing 2.65 at% in total of yttrium and gadolinium, with an yttrium to gadolinium ratio of 1.46:1. Additionally, it contained 0.12 at% Zr and 0.08 at% Zn, with other elements being at impurity levels.
  • Another magnesium alloy DF9380 was produced containing a a 3.03 at% of a mixture of erbium, gadolinium and yttrium with a soluble rare earth plus yttrium to gadolinium ratio of 1.38:1. Additionally it contained 0.125 at% zirconium.
  • All these alloys possessed yield stresses greater than 300MPa and elongations-to-failure greater than or equal to 10%.
  • DF8915 had a significantly higher ratio of 3.9:1 and this produced a reduced yield stress of only 250MPa.
  • DF9386 and DF8758 both had a significantly lower ratio of 0.72:1 and 0.93:1 respectively. These low ratios had the effect of reducing the ductility of these alloys to below 5% to levels that are commercially unacceptable for this type of product.
  • a further alloy magnesium alloy DF9381 was produced containing 2.99 at% of a mixture of ytterbium, gadolinium and yttrium with a soluble rare earth plus yttrium to gadolinium ratio of 1.39:1. Additionally it contained 0.121 at% zirconium.
  • the ytterbium in this alloy is not a soluble heavy lanthanide, and as a result of its addition to the alloy the strength of the alloy was reduced to unacceptably low levels.
  • a further set of test alloys were produced to examine the effect of zirconium on corrosion for the alloys of the present invention.
  • Melts DF9382a to DF9382e all had the same composition except for varying levels of zirconium. Alloy DF9382a shows that if the material is zirconium free (i.e. below detectable limits with standard industrial spark emission spectroscopy) the corrosion rate is above the acceptable level of 50 mils per year corrosion in the standard salt fog test. Further, at higher levels of zirconium for this alloy, DF9382b and DF9382c also show this poor behaviour. However at levels of zirconium between 0.03 at % (0.1 wt %) and 0.12 at % (0.4 wt%) good corrosion performance is achieved. This is demonstrated by DF9382d and DF9382e.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Forging (AREA)
  • Powder Metallurgy (AREA)
EP07804280A 2006-09-13 2007-09-12 Magnesium-gadolinium-legierungen Not-in-force EP2074236B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0617970.9A GB0617970D0 (en) 2006-09-13 2006-09-13 Magnesium gadolinium alloys
PCT/GB2007/003491 WO2008032087A2 (en) 2006-09-13 2007-09-12 Magnesium gadolinium alloys

Publications (2)

Publication Number Publication Date
EP2074236A2 true EP2074236A2 (de) 2009-07-01
EP2074236B1 EP2074236B1 (de) 2013-02-20

Family

ID=37232818

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07804280A Not-in-force EP2074236B1 (de) 2006-09-13 2007-09-12 Magnesium-gadolinium-legierungen

Country Status (12)

Country Link
US (1) US20090175754A1 (de)
EP (1) EP2074236B1 (de)
JP (1) JP5309031B2 (de)
KR (1) KR101350126B1 (de)
CN (1) CN101512029B (de)
BR (1) BRPI0716895A2 (de)
CA (1) CA2663605C (de)
GB (1) GB0617970D0 (de)
IL (1) IL197400A (de)
RU (1) RU2450068C2 (de)
TW (1) TWI426137B (de)
WO (1) WO2008032087A2 (de)

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GB0817893D0 (en) * 2008-09-30 2008-11-05 Magnesium Elektron Ltd Magnesium alloys containing rare earths
US11491257B2 (en) 2010-07-02 2022-11-08 University Of Florida Research Foundation, Inc. Bioresorbable metal alloy and implants
CN101857936B (zh) * 2010-07-05 2012-05-23 重庆大学 一种镁合金的制备方法
CN104195397B (zh) * 2014-09-10 2016-11-30 山西银光华盛镁业股份有限公司 一种高强耐热变形镁合金及其制造方法
WO2016118444A1 (en) * 2015-01-23 2016-07-28 University Of Florida Research Foundation, Inc. Radiation shielding and mitigating alloys, methods of manufacture thereof and articles comprising the same
RU2617072C2 (ru) * 2015-10-06 2017-04-19 Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) Литейный магниевый сплав с редкоземельными металлами
KR101876854B1 (ko) * 2016-08-12 2018-07-11 한국생산기술연구원 철 합금 탈산용 철-가돌리늄 이원합금
CN106282675B (zh) * 2016-08-29 2017-12-15 北京工业大学 一种低成本短流程高强稀土镁合金板材的制备技术
CN106191599A (zh) * 2016-09-23 2016-12-07 闻喜县瑞格镁业有限公司 一种高强度耐高温抗蠕变镁合金及其制备方法
RU2682191C1 (ru) * 2018-05-23 2019-03-15 федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" Лигатура для жаропрочных магниевых сплавов
CN113164659B (zh) * 2018-11-30 2023-08-25 尤安艾公司 生物降解性金属合金
KR102054191B1 (ko) * 2019-09-26 2020-01-22 유앤아이 주식회사 생체분해성 금속 합금
CN110229984B (zh) * 2019-06-20 2020-08-04 上海交通大学 一种高强度Mg-Gd-Er-Y镁合金及其制备方法
CN110964961A (zh) * 2019-12-31 2020-04-07 龙南龙钇重稀土科技股份有限公司 一种高强高耐腐蚀性镁合金及其制备工艺
CN113832371A (zh) * 2020-06-23 2021-12-24 宝山钢铁股份有限公司 一种高强镁合金挤压型材及其制造方法
CN113088778B (zh) * 2021-04-02 2022-02-08 北京理工大学 一种高强高刚度镁合金及其制备方法
CN113564440A (zh) * 2021-08-02 2021-10-29 西安四方超轻材料有限公司 一种高性能易锻造的镁合金材料及制备方法
CN115161504A (zh) * 2022-08-03 2022-10-11 重庆大学 一种基于Mg-Gd-Y制备高浓高性能镁合金的设计方法及镁合金
CN115300676A (zh) * 2022-08-08 2022-11-08 中南大学湘雅医院 一种载药医疗器械及其制备方法

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Also Published As

Publication number Publication date
JP2010503767A (ja) 2010-02-04
IL197400A (en) 2014-01-30
CN101512029B (zh) 2012-04-18
GB0617970D0 (en) 2006-10-18
US20090175754A1 (en) 2009-07-09
KR20090055028A (ko) 2009-06-01
TWI426137B (zh) 2014-02-11
WO2008032087A3 (en) 2008-05-22
CA2663605A1 (en) 2008-03-20
IL197400A0 (en) 2009-12-24
KR101350126B1 (ko) 2014-01-15
EP2074236B1 (de) 2013-02-20
RU2450068C2 (ru) 2012-05-10
TW200821392A (en) 2008-05-16
CN101512029A (zh) 2009-08-19
CA2663605C (en) 2016-07-19
BRPI0716895A2 (pt) 2013-10-22
JP5309031B2 (ja) 2013-10-09
WO2008032087A2 (en) 2008-03-20
RU2009113576A (ru) 2010-10-20

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