WO2008032857A1 - Alliage de magnésium hautement résistant et son procédé de fabrication - Google Patents

Alliage de magnésium hautement résistant et son procédé de fabrication Download PDF

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Publication number
WO2008032857A1
WO2008032857A1 PCT/JP2007/068214 JP2007068214W WO2008032857A1 WO 2008032857 A1 WO2008032857 A1 WO 2008032857A1 JP 2007068214 W JP2007068214 W JP 2007068214W WO 2008032857 A1 WO2008032857 A1 WO 2008032857A1
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WO
WIPO (PCT)
Prior art keywords
alloy
molten
magnesium alloy
quasicrystals
strength magnesium
Prior art date
Application number
PCT/JP2007/068214
Other languages
English (en)
Japanese (ja)
Inventor
An Pang Tsai
Satoshi Ohhashi
Akira Kato
Original Assignee
Toyota Jidosha Kabushiki Kaisha
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 Toyota Jidosha Kabushiki Kaisha filed Critical Toyota Jidosha Kabushiki Kaisha
Priority to US12/375,691 priority Critical patent/US20090320967A1/en
Priority to CN2007800278886A priority patent/CN101495660B/zh
Publication of WO2008032857A1 publication Critical patent/WO2008032857A1/fr

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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
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • the present invention relates to a high-strength magnesium alloy, in particular, a magnesium alloy with increased high-temperature strength and a method for producing the same.
  • Magnesium alloys are being applied to various structural members by taking advantage of their light weight. In particular, when applied to automobiles, it is effective in improving fuel consumption and thereby protecting resources and the environment.
  • AZ 9 1 C and ZE 4 1 A which are sand-type forging alloys, are precipitation effect type alloys, and T 6 (solution + aging) or T 5 (aging only) is applied to the forging material. Adjust to the required strength.
  • T 6 solution + aging
  • T 5 aging only
  • AZ 6 1 A and AZ 3 1 B which are wrought alloys, use the grain refinement by processing and recrystallization during rolling, extrusion, etc. as a strengthening mechanism. ing.
  • the temperature is higher than 100 ° C, remarkable grain boundary slippage unique to Mg occurs, so the refinement of crystal grains conversely causes a decrease in strength due to an increase in the generation site of grain boundary slippage. .
  • crystal grains grow and the effect of refining is lost, causing a decrease in room temperature strength. As a result, not only high temperature strength could not be secured, but also room temperature strength was thermally unstable.
  • Japanese Patent Application Laid-Open No. 2002-309332 discloses Mg-1 to 10 at% Zn— in which a solid solution matrix is dispersed and strengthened with quasicrystalline particles. 0. l-3at% Y alloy is disclosed.
  • a quasicrystalline eutectic structure is formed at the ⁇ -Mg grain boundary, and the quasicrystal is finely and uniformly dispersed by hot working. Because quasicrystals are much harder than crystalline compounds of approximate composition, magnesium with excellent strength and stretchability can be obtained.
  • the thermal stability has increased, the strength itself is comparable to that of a commercially available alloy with a similar composition such as Z E 41, and there is a limit that a higher high-temperature strength cannot be obtained.
  • the JP 2 0 0 5 1 1 3 2 3 5 JP contrast, as an alloy with improved high temperature strength, M g, 0 0., a + b) Z n a Y b, a / 1 2 ⁇ b ⁇ a Z 3 and 1.5 ⁇ a ⁇ 1 0, and its approximate crystal with Mg 3 Z n 6 quasicrystal in Mg parent phase (complex structure phase derived from quasicrystal)
  • Mg 3 Z n 6 quasicrystal in Mg parent phase complex structure phase derived from quasicrystal
  • JP-2 0 0 6 - 8 9 7 7 2 discloses, M g 1 M _ (a + b + c) Z n a Z r b Y. , A / 1 2 ⁇ (b + c) ⁇ a / 3 and 1.5 ⁇ a ⁇ 1 0, 0. 0 5 ⁇ b ⁇ 0. 2 5 c, similar to Mg matrix A magnesium alloy in which fine particles of crystals are dispersed is disclosed.
  • Mg 3 Z n 6 A magnesium alloy in which the approximate crystal (complex structure phase derived from a quasicrystal) is dispersed in the form of fine particles is disclosed.
  • An object of the present invention is to provide a high-strength magnesium alloy that is inexpensive and improves high-temperature strength without using expensive rare earth elements, and a method for producing the same.
  • the high-strength magnesium alloy of the first invention is represented by the composition formula M g 1 () () -( a + b ) Z n a X b , where X is Z r, T 1 or more selected from i and H f, a and b are the contents of Zn and X, respectively, expressed in at%, and the relationship of the following formulas (1), (2) and (3): a / 2 8 ⁇ b ⁇ a / 9---(1)
  • the Mg-Zn-X quasicrystal and its approximate crystal are dispersed in the form of fine particles in the Mg matrix.
  • the method of the second invention for producing the high-strength magnesium alloy of the first invention is as follows: A process of melting Mg in an inert atmosphere to form a molten Mg, in which the Mg-Zn-X series quasicrystal (X is one of Zr, Ti, Hf) A process of forming a molten alloy,
  • the obtained forged product is heat treated to precipitate the quasicrystal and its approximate crystal in an Mg matrix.
  • the high-strength magnesium alloy of the present invention is a conventional rare earth element obtained by dispersing Mg-Zn-X quasicrystals in the form of fine particles and their approximate crystals as reinforcing particles in an Mg matrix. Can achieve high strength, especially high temperature strength, equivalent to alloys in which quasicrystals and approximate crystals are dispersed using
  • M g manufactured according to this invention is a photograph of electron beam diffraction pattern of Z n 83 Z r 6 quasicrystal.
  • FIG. 2 is a transmission electron micrograph showing the metal structure of the Mg alloy produced according to the present invention.
  • a quasicrystal is a compound that has a regular structure (typically 5-fold symmetry) in the short range, but does not have the translational symmetry characteristic of ordinary crystals.
  • the compositions that produce quasicrystals are known as A 1 — P d — M n, A 1 — C u — F e, C d — Y b, M g — Z n — Y, etc. It is. Because of its unique structure, it has various unique properties such as high hardness, high melting point, and low friction coefficient compared to crystalline intermetallic compounds of approximate composition.
  • An approximate crystal is a crystalline compound that has a complex structure derived from a quasicrystal, partially having the same structure as the quasicrystal, and has the same properties as the quasicrystal from which it was derived.
  • the fine particles have a particle size of about several tens of nm to several hundreds of nm.
  • Quasicrystals and approximate crystals are very hard and stable without decomposition up to about 230 ° C, so if they are dispersed as fine particles in the Mg matrix, they strongly interact with dislocations. Acts and exhibits extremely high dispersion strengthening action, improving the strength at normal and high temperatures. In particular, the fine particles present in the Hi-Mg grain boundary suppress grain boundary sliding at high temperatures and contribute to high high-temperature strength.
  • the alloy of the present invention uses Zr, Ti, and Hf as constituents of the quasicrystal and the approximate crystal in place of the conventional rare earth alloy, but these elements are combined with the molten Mg, which is the main component of the alloy. Since it is difficult to melt, it cannot be produced by directly melting a molten alloy of the final composition like a conventional alloy containing rare earth elements. That is, even if the raw materials of each alloy component are weighed according to the final alloy composition, charged together in a melting furnace and heated to form a molten metal, the high melting points Zr, Ti, and Hf are It does not dissolve in the molten metal and remains as a solid. These refractory elements have very high melting points, higher than the boiling point of Mg.
  • the rare earth elements such as Y used in conventional alloys themselves have a much higher melting point than Mg, but they are alloyed by contact with the molten Mg produced earlier at low temperatures during melting.
  • the conventional alloy was able to directly melt the molten metal with the final composition because it was easily converted into Mg melt.
  • the alloy of the present invention cannot directly melt the molten alloy of the final composition as described above, in the method of the present invention, only Mg is melted to form a Mg melt, and a quasicrystal It was possible to form molten alloy by adding. The amount of Mg melt, the composition of the quasicrystal and the amount added, to adjust the final alloy composition. Thoroughly stir the molten alloy into a uniform melt.
  • the obtained molten alloy is formed by a usual method.
  • the resulting fabricated product is heat treated to precipitate quasicrystals and approximate crystals as fine particles in the Mg matrix.
  • the molten alloy with quasicrystals added and sufficiently stirred in the molten Mg is visually uniform, but microscopically there is a composition fluctuation in the molten metal, and there is a fine region in which the specific elements are unevenly distributed.
  • the quasicrystal and approximate crystal or its precursor composition crystallize finely in the cooling process during fabrication, with this finely distributed region as the nucleus.
  • the solidified product is a supersaturated solid solution of Zn and X (one or more of Z r, T i, and H f), which are constituent elements of quasicrystals or approximate crystals, in the Mg matrix. By heat treatment, quasi-crystals or approximate crystals are precipitated as fine particles with fine crystals as nuclei.
  • an Mg-Zn—Zr magnesium alloy having the final composition of the entire alloy shown in Table 1 was prepared, and the metal structure was observed and a tensile test was performed.
  • the obtained massive quasicrystal was pulverized to a particle size of several tens; m and used for the following.
  • Pure Mg (purity 99.99%) was charged into a graphite crucible and melted by raising the temperature to 70 0 in a high-frequency melting furnace held in an argon atmosphere to form an Mg melt.
  • the obtained molten alloy was kept at 700 ° C. and poured into a pig iron J IS 4 No. 4 ship type (70 mm ⁇ 70 mm ⁇ 300 mm) preheated to about 100 ° C.
  • the fabricated product obtained above was heat-treated at 50 ° C. for 48 hours under an argon atmosphere.
  • a round bar tensile test piece having a parallel portion of ⁇ 5 X 25 mm was collected and subjected to a tensile test at room temperature, 1550 ° C and 2100 ° C.
  • the tensile speed was 0.8 mm / min.
  • the final composition of the entire alloy is the composition shown in Table 1 Mg
  • One Z n—Ti magnesium alloy was fabricated and fx of metal structure observation and tensile tests were performed.
  • the material of the present invention is particularly excellent in tensile strength at 150 ° C compared to the conventional material.
  • the decrease in strength accompanying the temperature increase from room temperature to 1550 ° C is very small. This is because — Fine particles composed of quasicrystals and approximate crystals precipitated and dispersed in Mg grains are very thermally stable, so they interact strongly with dislocations even at high temperatures of 150 ° C. This is because it functions effectively as a barrier to dislocation movement.
  • Comparative materials with a composition outside the scope of the present invention do not produce quasicrystals or approximate crystals, or even if they are produced, the amount of dispersion strengthening by these produced phases is hardly obtained. High strength cannot be obtained.
  • a high-strength magnesium alloy which is reduced in price without using an expensive rare earth element and improved in high-temperature strength and a method for producing the same.

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

Abstract

La présente invention concerne un alliage de magnésium hautement résistant amélioré du point de vue de la résistance aux hautes températures, ne nécessitant pas l'utilisation de lanthanides coûteux et permettant ainsi une réduction du coût, ainsi qu'un procédé de fabrication dudit alliage. L'invention concerne un alliage de magnésium hautement résistant représenté par la formule de composition suivante : Mg100-(a+b)ZnaXb (où X est au moins un élément sélectionné parmi Zr, Ti et Hf et a et b sont les teneurs respectives de Zn et X représentées en pourcentage at. et satisfont aux relations (1), (2) et (3): (1) a/28 ≤ b ≤ a/9, (2) 2 < a < 10, et (3) 0,05 < b < 1,0), où des quasicristaux Mg-Zn-X et des approximants de ceux-ci sous la forme de fines particules sont dispersés dans une phase de Mg ; ainsi qu'un procédé de fabrication de l'alliage de magnésium hautement résistant comprenant les étapes consistant à faire fondre le Mg dans une atmosphère inerte en vue de produire un Mg à l'état fondu, à ajouter des quasicristaux Mg-Zn-X (où X est au moins Zr, Ti et/ou Hf) au Mg à l'état fondu en vue de former un alliage à l'état fondu, à couler l'alliage à l'état fondu et à procéder au traitement thermique de l'alliage coulé en vue de précipiter les quasicristaux et les approximants de ceux-ci dans la phase matricielle de Mg.
PCT/JP2007/068214 2006-09-15 2007-09-12 Alliage de magnésium hautement résistant et son procédé de fabrication WO2008032857A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/375,691 US20090320967A1 (en) 2006-09-15 2007-09-12 High strength magnesium alloy and method of production of the same
CN2007800278886A CN101495660B (zh) 2006-09-15 2007-09-12 高强度镁合金及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006251434A JP4849402B2 (ja) 2006-09-15 2006-09-15 高強度マグネシウム合金およびその製造方法
JP2006-251434 2006-09-15

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WO2008032857A1 true WO2008032857A1 (fr) 2008-03-20

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US (1) US20090320967A1 (fr)
JP (1) JP4849402B2 (fr)
CN (1) CN101495660B (fr)
WO (1) WO2008032857A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102242300A (zh) * 2011-08-23 2011-11-16 中国兵器工业第五九研究所 一种高强韧耐蚀镁合金及其制备方法

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Publication number Priority date Publication date Assignee Title
JP5403508B2 (ja) * 2009-03-24 2014-01-29 独立行政法人物質・材料研究機構 Ｍｇ合金部材。
CN101787475B (zh) * 2010-03-22 2011-09-07 北京工业大学 准晶颗粒增强镁基复合材料及其制备方法
CN102618770B (zh) * 2012-03-27 2013-11-06 北京工业大学 一种超高强多用途轻质合金、熔炼工艺及应用
KR101807985B1 (ko) 2014-03-28 2017-12-11 신닛테츠스미킨 카부시키카이샤 준결정 함유 도금 강판
AU2014388691B2 (en) 2014-03-28 2017-08-03 Nippon Steel Corporation Plated steel sheet containing quasicrystal
KR101890078B1 (ko) 2014-09-05 2018-08-20 신닛테츠스미킨 카부시키카이샤 준결정 함유 도금 강판 및 준결정 함유 도금 강판의 제조 방법
CN104451312B (zh) * 2014-11-11 2016-11-23 沈阳航空航天大学 含微量高熔点元素的高比强度镁合金及其制备方法
CN105331866B (zh) * 2015-10-14 2017-06-23 济南大学 一种Mg‑Zn‑Gd准晶增强的AZ91镁合金及其制备方法
CN106350720B (zh) * 2016-10-17 2017-12-22 南京镐极信息技术有限公司 含铪耐热铸造镁合金及其制备方法
CN110846687A (zh) * 2019-11-22 2020-02-28 龙南龙钇重稀土科技股份有限公司 一种Mg-Zn-Zr中间合金及其制备方法
EP4303333A4 (fr) 2021-03-29 2024-10-02 Univ Tokyo Science Found Alliage d'or et procédé de production d'alliage d'or

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JP2002309332A (ja) * 2001-04-11 2002-10-23 Yonsei Univ 熱間成形性の優れた準結晶相強化マグネシウム系合金
JP2005113234A (ja) * 2003-10-09 2005-04-28 Toyota Motor Corp 高強度マグネシウム合金およびその製造方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102242300A (zh) * 2011-08-23 2011-11-16 中国兵器工业第五九研究所 一种高强韧耐蚀镁合金及其制备方法

Also Published As

Publication number Publication date
CN101495660A (zh) 2009-07-29
CN101495660B (zh) 2010-11-10
JP2008069438A (ja) 2008-03-27
JP4849402B2 (ja) 2012-01-11
US20090320967A1 (en) 2009-12-31

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