EP0470599A1 - Hochfeste Legierungen auf Magnesiumbasis - Google Patents

Hochfeste Legierungen auf Magnesiumbasis Download PDF

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Publication number
EP0470599A1
EP0470599A1 EP91113280A EP91113280A EP0470599A1 EP 0470599 A1 EP0470599 A1 EP 0470599A1 EP 91113280 A EP91113280 A EP 91113280A EP 91113280 A EP91113280 A EP 91113280A EP 0470599 A1 EP0470599 A1 EP 0470599A1
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EP
European Patent Office
Prior art keywords
alloy
matrix
group
elements
element selected
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.)
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Application number
EP91113280A
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English (en)
French (fr)
Inventor
Kazuo Aikawa
Katsuyuki Taketni
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YKK Corp
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YKK Corp
Yoshida Kogyo KK
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Application filed by YKK Corp, Yoshida Kogyo KK filed Critical YKK Corp
Publication of EP0470599A1 publication Critical patent/EP0470599A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/005—Amorphous alloys with Mg as the 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
    • C22C1/11—Making amorphous alloys
    • 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
    • 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
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent

Definitions

  • the present invention relates to aluminum-based alloys having superior hardness and strength together with high corrosion resistance.
  • amorphous magnesium-based alloys As conventional amorphous magnesium-based alloys, for example, an amorphous magnesium-based alloys has been proposed in Japanese Patent Application Laid-Open No. 3 - 10041. Known magnesium-based alloys have all been produced in order to form an amorphous single-phase structure and thereby obtain an enhanced strength.
  • the amorphous magnesium based alloy described in the above Japanese Patent Application Laid-Open No. 3 - 10041 exhibits superior properties such as high strength and high hardness, and, thus, it is especially superior as a high strength material.
  • the present inventors considered that the strength and hardness of alloy materials would be still improved by directing their attention to the ratio between the amorphous phase and the crystalline phase in the alloy materials.
  • magnesium-based alloys which are further improved in their hardness and strength by investigating in detail the amorphous phase and the crystalline phase existing therein.
  • La, Ce, Nd and Sm may be replaced with misch metal (Mm) which contains these elements as main components.
  • Mm used herein is intended to mean a composite comprising, in atomic percentage, 40 to 50% Ce and 20 to 25% La and the balance being other rare earth elements and tolerable levels of impurities (e.g., Mg, Al, Si and Fe, etc.).
  • the Mm may be substituted by the other Ln elements in an Mm : Ln ratio of 1 : 1 (by atomic percent).
  • the Mm is a highly cost-effective source for the Ln alloying elements because of its cheap price.
  • the single figure shows a schematic illustration of a single-roller melt spinning apparatus employed to prepare thin ribbons by rapidly quenching and solidifying alloys of the present invention.
  • the magnesium-based alloys of the present invention can be obtained by rapidly solidifying a melt of the alloy having the composition as specified above, employing liquid quenching techniques.
  • the liquid quenching techniques are methods for rapidly cooling a molten alloy and, particularly, single-roller melt-spinning, twin-roller melt-spinning and in-rotating-water melt-spinning are effective. In these techniques, a cooling rate of about 10 4 to 10 6 K/sec can be obtained.
  • the molten alloy 3 is ejected from the bore 5 of a nozzle 1 onto a roll 2 of, for example, copper or steel, with a diameter of about 30 - 3000 mm, which is rotating at a constant rate within the range of about 300 - 10000 rpm.
  • various thin ribbon materials with a width of about 1 - 300 mm and a thickness of about 5 - 500 /1.m can be readily obtained.
  • a jet of the molten alloy is directed, under application of a back pressure of argon gas, through a nozzle into a liquid refrigerant layer having a depth of about 1 to 10 cm which is held by centrifugal force in a drum rotating at a rate of about 50 to 500 rpm.
  • the angle between the molten alloy ejecting from the nozzle and the liquid refrigerant surface is preferably in the range of about 60 to 90 and the relative velocity ratio of the ejected molten alloy to the liquid refrigerant surface is preferably in the range of about 0.7 to 0.9.
  • the alloy of the present invention may also be obtained by firstly forming an amorphous alloy in the same procedure as described above, except employing a slightly increased cooling rate, and, then, heating the resultant amorphous alloy to the vicinity of its crystallization temperature (crystallization temperature ⁇ 100 C), thereby causing crystallization.
  • the intended alloys can be produced at temperatures lower than 100 ° C less than their crystallization temperature.
  • the alloy of the present invention can also be obtained in the form of a thin film by sputtering. Further, rapidly solidified powder of the alloy composition of the present invention can be obtained by various atomizing processes (e.g., high pressure gas atomizing), spraying, mechanical alloying, mechanical grinding, etc.
  • a is limited to the range of 40 to 95 atomic % and b is limited to the range of 5 to 60 atomic %.
  • the reason for such limitations is that when a and b are outside the specified ranges, it is difficult to form a supersaturated solid solution containing therein solute elements in amounts exceeding their solid solubility limits and amorphization becomes difficult. Consequently, alloys having properties contemplated by the present invention can not be obtained by industrial rapid quenching processes employing the above-mentioned liquid quenching or the like.
  • a, c and d are limited to the atomic percentages ranging from 40 to 95%, 1 to 35% and 1 to 25%, respectively.
  • the reason for such limitations is that when a, c and d are outside the specified ranges, it is difficult to form a supersaturated solid solution containing therein solute elements in amounts exceeding their solid solubility limits and amorphization becomes difficult. Consequently, alloys having properties contemplated by the present invention can not be obtained by industrial rapid quenching processes employing the foregoing liquid quenching or the like.
  • a, c and e are limited to the atomic percentages ranging from 40 to 95%, 1 to 35% and 3 to 25%, respectively.
  • the reason for such limitations is that when a, c and e are outside the specified ranges, it is difficult to form a supersaturated solid solution containing therein solute elements in amounts exceeding their solid solubility limits and amorphization partially becomes difficult. Consequently, alloys having properties contemplated by the present invention can not be obtained by industrial rapid quenching processes employing the above liquid quenching or the like.
  • a, c, d and e are limited to the atomic percentages ranging from 40 to 95%, 1 to 35%, 1 to 25% and 3 to 25%, respectively.
  • the reason for such limitations is that when a, c, d and e are outside the specified ranges, it is difficult to form a supersaturated solid solution containing therein solute elements in amounts exceeding their solid solubility limits and amorphization becomes difficult. Consequently, alloys having properties contemplated by the present invention can not be obtained by industrial rapid quenching processes employing the above-mentioned liquid quenching or the like.
  • the X element is at least one element selected from the group consisting of Cu, Ni, Sn and Zn.
  • the X element exhibits superior effects in stabilizing the resulting fine crystalline phase and improving the amorphous-forming ability, under the conditions of the preparation of the alloys of the present invention.
  • the X element has a strengthening effect while retaining the ductility.
  • the M element is at least one element selected from the group consisting of Al, Si and Ca and forms stable or metastable intermetallic compounds in combination with Mg or other additive elements in the fine crystalline phase of the present invention.
  • the intermetallic compounds thus formed are uniformly and finely distributed throughout a magnesium matrix (a -phase), and, thereby, considerably improve the hardness and strength of the resultant alloys.
  • the M element further prevents coarsening of the fine crystalline phase at high temperatures and provides a good heat resistance. Also, the M element also stabilizes the amorphous phase at relatively elevated temperatures.
  • AI and Ca have an effect of improving the corrosion resistance and Si improves the fluidity of the molten alloy.
  • the Ln element is at least one element selected from the group consisting of Y, La, Ce, Nd and Sm or a misch metal (Mm) which is a mixture of rare earth elements. Addition of the Ln element to the Mg-X system or the Mg-X-M system alloys develops a further stabilized fine crystalline phase in these alloys and makes possible great improvement in their hardness. In the amorphous phase, the Ln element exhibits a significant effect of improving the amorphous-phase forming ability.
  • Mm misch metal
  • the magnesium-based alloys of the present invention show superplasticity in the vicinity of their crystallization temperature (Tx ⁇ 100 C), they can be readily processed by extrusion, press working, hot-forging, etc. Therefore, the magnesium-based alloys of the present invention, obtained in the form of thin ribbons, wires, sheets or powder, can be successfully formed into bulk materials by extrusion, press working, hot-forging, etc., within the range of Tx ⁇ 100 C. Further, some of the magnesium-based alloys of the present invention are sufficiently ductile to permit a high degree of bending.
  • Molten alloy 3 having a predetermined composition, was prepared using a high-frequency melting furnace and charged into a quartz tube 1 having a small opening 5 (diameter: 0.5 mm) at the tip thereof, as shown in the drawing. After being heated to melt the alloy 3, the quartz tube 1 was disposed right above a copper roll 2. Then, the molten alloy 3 contained in the quartz tube 1 was ejected from the small opening 5 of the quartz tube 1, under the application of an argon gas pressure of 0.7 kg/cm 2 , and brought into contact with the surface of the copper roll 2 rapidly rotating at a rate of 5,000 rpm. The molten alloy 3 was rapidly quenched and solidified into an alloy thin ribbon 4.
  • the hardness (Hv) is indicated by values (DPN) measured using a microVickers hardness tester under a load of 25 g.
  • test specimens showed a high level of hardness Hv (DPN) of at least 185 which is about 2.0 to 3.0 times the hardness Hv (DPN), i.e., 60 - 90, of the conventional magnesium-based alloys. Further, the test specimens of the present invention all exhibited a high tensile-strength level of not less than 630 MPa and such a high strength level is at least approximately 1.5 times the highest strength level of 400 MPa achieved in known magnesium-based alloys. It can be seen from such results that the alloy materials of the present invention are superior in hardness and strength.
  • the magnesium-based alloy of the present invention have a high hardness and a high strength which are, respectively, at least 2.0 times and at least 1.5 times those of a similar type of magnesium-based alloy which has been heretofore evaluated as the most superior alloy and yet also have a good processability permitting extrusion or similar operations. Therefore, the alloys of the present invention exhibit advantageous effects in a wide variety of industrial applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
  • Powder Metallurgy (AREA)
EP91113280A 1990-08-09 1991-08-07 Hochfeste Legierungen auf Magnesiumbasis Withdrawn EP0470599A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP209159/90 1990-08-09
JP2209159A JPH0499244A (ja) 1990-08-09 1990-08-09 高力マグネシウム基合金

Publications (1)

Publication Number Publication Date
EP0470599A1 true EP0470599A1 (de) 1992-02-12

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EP91113280A Withdrawn EP0470599A1 (de) 1990-08-09 1991-08-07 Hochfeste Legierungen auf Magnesiumbasis

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JP (1) JPH0499244A (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548875A1 (de) * 1991-12-26 1993-06-30 Ykk Corporation Hochfeste Legierungen auf Magnesiumbasis
EP0661384A1 (de) * 1993-12-03 1995-07-05 Toyota Jidosha Kabushiki Kaisha Hitzebeständige Magnesiumlegierung
US5552110A (en) * 1991-07-26 1996-09-03 Toyota Jidosha Kabushiki Kaisha Heat resistant magnesium alloy
EP0531165B1 (de) * 1991-09-06 1998-04-29 Tsuyoshi Masumoto Hochfeste amorphe Magnesiumlegierung und Verfahren zu ihrer Herstellung
EP1111082A1 (de) * 1999-11-18 2001-06-27 Ykk Corporation Geformter Artikel aus einer amorphen Legierung, mit gehärteter Oberfläche und Verfahren zu dessen Herstellung
WO2002072905A1 (en) * 2001-03-13 2002-09-19 Forskningscenter Risø A method of producing articles with fine outlines by way of shaping and crystallizing armophous alloys
EP2295613A1 (de) * 2008-06-03 2011-03-16 National Institute for Materials Science LEGIERUNG AUF Mg-BASIS
WO2016016628A3 (en) * 2014-07-28 2016-03-31 Magnesium Elektron Limited Corrodible downhole article
CN109504884A (zh) * 2019-01-10 2019-03-22 吉林大学 多元少量高强塑性镁合金及其大压下量短流程制备方法
US10329653B2 (en) 2014-04-18 2019-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools
US10625336B2 (en) 2014-02-21 2020-04-21 Terves, Llc Manufacture of controlled rate dissolving materials
US10689740B2 (en) 2014-04-18 2020-06-23 Terves, LLCq Galvanically-active in situ formed particles for controlled rate dissolving tools
US10758974B2 (en) 2014-02-21 2020-09-01 Terves, Llc Self-actuating device for centralizing an object
US10865465B2 (en) 2017-07-27 2020-12-15 Terves, Llc Degradable metal matrix composite
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
US11674208B2 (en) 2014-02-21 2023-06-13 Terves, Llc High conductivity magnesium alloy
US12018356B2 (en) 2020-06-08 2024-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002649B (zh) * 2010-09-16 2013-08-14 南京理工大学 高强韧镁基块体金属玻璃复合材料及其制备方法
JP7315941B2 (ja) * 2018-10-03 2023-07-27 地方独立行政法人東京都立産業技術研究センター 粉末材料、及びマグネシウム合金部材の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0361136A1 (de) * 1988-09-05 1990-04-04 Yoshida Kogyo K.K. Hochfeste Legierungen auf Magnesiumbasis
EP0407964A2 (de) * 1989-07-13 1991-01-16 Ykk Corporation Hochfeste Legierungen auf Magnesium-Basis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0361136A1 (de) * 1988-09-05 1990-04-04 Yoshida Kogyo K.K. Hochfeste Legierungen auf Magnesiumbasis
EP0407964A2 (de) * 1989-07-13 1991-01-16 Ykk Corporation Hochfeste Legierungen auf Magnesium-Basis

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5552110A (en) * 1991-07-26 1996-09-03 Toyota Jidosha Kabushiki Kaisha Heat resistant magnesium alloy
EP0531165B1 (de) * 1991-09-06 1998-04-29 Tsuyoshi Masumoto Hochfeste amorphe Magnesiumlegierung und Verfahren zu ihrer Herstellung
EP0548875A1 (de) * 1991-12-26 1993-06-30 Ykk Corporation Hochfeste Legierungen auf Magnesiumbasis
EP0661384A1 (de) * 1993-12-03 1995-07-05 Toyota Jidosha Kabushiki Kaisha Hitzebeständige Magnesiumlegierung
CN1041000C (zh) * 1993-12-03 1998-12-02 丰田自动车株式会社 耐热镁合金
EP1111082A1 (de) * 1999-11-18 2001-06-27 Ykk Corporation Geformter Artikel aus einer amorphen Legierung, mit gehärteter Oberfläche und Verfahren zu dessen Herstellung
US6530998B1 (en) 1999-11-18 2003-03-11 Ykk Corporation Formed article of amorphous alloy having hardened surface and method for production thereof
CN1309858C (zh) * 1999-11-18 2007-04-11 Ykk株式会社 具有硬化表面的非晶态合金成型件及其生产方法
WO2002072905A1 (en) * 2001-03-13 2002-09-19 Forskningscenter Risø A method of producing articles with fine outlines by way of shaping and crystallizing armophous alloys
EP2295613A1 (de) * 2008-06-03 2011-03-16 National Institute for Materials Science LEGIERUNG AUF Mg-BASIS
EP2295613A4 (de) * 2008-06-03 2013-07-24 Nat Inst For Materials Science LEGIERUNG AUF Mg-BASIS
US10625336B2 (en) 2014-02-21 2020-04-21 Terves, Llc Manufacture of controlled rate dissolving materials
US10758974B2 (en) 2014-02-21 2020-09-01 Terves, Llc Self-actuating device for centralizing an object
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US11097338B2 (en) 2014-02-21 2021-08-24 Terves, Llc Self-actuating device for centralizing an object
US11674208B2 (en) 2014-02-21 2023-06-13 Terves, Llc High conductivity magnesium alloy
US11613952B2 (en) 2014-02-21 2023-03-28 Terves, Llc Fluid activated disintegrating metal system
US11685983B2 (en) 2014-02-21 2023-06-27 Terves, Llc High conductivity magnesium alloy
US10724128B2 (en) 2014-04-18 2020-07-28 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US10760151B2 (en) 2014-04-18 2020-09-01 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US10689740B2 (en) 2014-04-18 2020-06-23 Terves, LLCq Galvanically-active in situ formed particles for controlled rate dissolving tools
US10329653B2 (en) 2014-04-18 2019-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools
WO2016016628A3 (en) * 2014-07-28 2016-03-31 Magnesium Elektron Limited Corrodible downhole article
US10337086B2 (en) 2014-07-28 2019-07-02 Magnesium Elektron Limited Corrodible downhole article
US10329643B2 (en) 2014-07-28 2019-06-25 Magnesium Elektron Limited Corrodible downhole article
US10865465B2 (en) 2017-07-27 2020-12-15 Terves, Llc Degradable metal matrix composite
US11649526B2 (en) 2017-07-27 2023-05-16 Terves, Llc Degradable metal matrix composite
US11898223B2 (en) 2017-07-27 2024-02-13 Terves, Llc Degradable metal matrix composite
CN109504884A (zh) * 2019-01-10 2019-03-22 吉林大学 多元少量高强塑性镁合金及其大压下量短流程制备方法
CN109504884B (zh) * 2019-01-10 2020-07-28 吉林大学 多元少量高强塑性镁合金及其大压下量短流程制备方法
US12018356B2 (en) 2020-06-08 2024-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools

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Publication number Publication date
JPH0499244A (ja) 1992-03-31

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