US20040112475A1 - Cu-base amorphous alloy - Google Patents

Cu-base amorphous alloy Download PDF

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Publication number
US20040112475A1
US20040112475A1 US10/451,143 US45114303A US2004112475A1 US 20040112475 A1 US20040112475 A1 US 20040112475A1 US 45114303 A US45114303 A US 45114303A US 2004112475 A1 US2004112475 A1 US 2004112475A1
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Prior art keywords
alloy
amorphous
amorphous phase
amorphous alloy
inventive example
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US10/451,143
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English (en)
Inventor
Akihisa Inoue
Wei Zhang
Tao Zhang
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Japan Science and Technology Agency
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Japan Science and Technology Agency
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Assigned to JAPAN SCIENCE AND TECHNOLOGY CORPORATION reassignment JAPAN SCIENCE AND TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ZHANG, TAO, INOUE, AKIHISA, ZHANG, WEI
Publication of US20040112475A1 publication Critical patent/US20040112475A1/en
Assigned to JAPAN SCIENCE AND TECHNOLOGY AGENCY reassignment JAPAN SCIENCE AND TECHNOLOGY AGENCY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: JAPAN SCIENCE AND TECHNOLOGY CORPORATION
Priority to US12/292,723 priority Critical patent/US8470103B2/en
Abandoned legal-status Critical Current

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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
    • C22C45/001—Amorphous alloys with Cu 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

Definitions

  • the present invention relates to a Cu-base amorphous alloy having a high glass-forming ability as well as excellent mechanical properties and formability.
  • an alloy in its molten state can be rapidly cooled or quenched to obtain an amorphous solid in various forms, such as thin strip, filament or powder/particle.
  • An amorphous alloy thin-strip or powder can be prepared through various processes, such as a single-roll process, a twin-roll process, an in-rotating liquid spinning process and an atomization process, which can provide a high quenching rate.
  • a number of Fe, Ti, Co, Zr, Ni, Pd or Cu-base amorphous alloys have been developed, and their specific properties such as excellent mechanical properties and high corrosion resistance have been clarified.
  • an amorphous alloy undergoing a glass transition with a wide supercooled liquid region and having a high reduced-glass-transition temperature (Tg/Tm) exhibits an excellent stability against crystallization and a high glass-forming ability.
  • the alloy having such a high glass-forming ability can be formed as a bulk amorphous alloy through a metal mold casting process. It is also known that when a specific amorphous alloy is heated, the viscosity of the amorphous alloy is sharply lowered during transition to the supercooled liquid state before crystallization.
  • Such an amorphous alloy can be formed in an arbitrary shape through a closed forging process or the like by taking advantage of the lowered viscosity in the supercooled liquid state.
  • an alloy having a wide supercooled liquid region and a high reduced-glass-transition temperature (Tg/Tm) exhibits a high glass-forming ability and an excellent formability.
  • the conventional Cu-base amorphous alloys have a poor glass-forming ability, and have been able to be formed only in limited forms, such as thin strip, powder and thin line, through a liquid quenching process. In addition, they have no stability at high temperature, and have difficulty in being converted into a final product with a desired shape, resulting in their quite limited industrial applications.
  • a Cu-base alloy having a specific composition containing Zr and/or Hf can be molten and then rapidly solidified from the liquid state to obtain a Cu-base amorphous alloy having a high glass-forming ability as well as excellent mechanical properties and formability, such as a rod-shaped (or plate-shaped) amorphous- phase material with 1 mm or more of diameter (or thickness).
  • a rod-shaped (or plate-shaped) amorphous- phase material with 1 mm or more of diameter (or thickness).
  • a Cu-base amorphous alloy comprising an amorphous phase of 90% or more by volume fraction.
  • the amorphous phase has a composition represented by the following formula:
  • a and b are atomic percentages falling within the following ranges: 5 ⁇ a ⁇ 55, 0 ⁇ b ⁇ 45, 30 ⁇ a+b ⁇ 60 .
  • (Zr+Hf) means Zr and/or Hf.
  • a Cu-base amorphous alloy comprising an amorphous phase of 90% or more by volume fraction.
  • the amorphous phase has a composition represented by the following formula:
  • a and b are atomic percentages falling within the following ranges: 10 ⁇ a ⁇ 40, 5 ⁇ b ⁇ 30, 35 ⁇ a+b ⁇ 50.
  • a Cu-base amorphous alloy comprising an amorphous phase of 90% or more by volume fraction.
  • the amorphous phase has a composition represented by the following formula:
  • M is one or more elements selected from the group consisting of Fe, Cr, Mn, Ni, Co, Nb, Mo, W, Sn, Al, Ta and rare earth elements
  • T is one or more elements selected from the group consisting of Ag, Pd, Pt and Au
  • a, b, c and d are atomic percentages falling within the following ranges: 5 ⁇ a ⁇ 55, 0 ⁇ b ⁇ 45, 30 ⁇ a+b ⁇ 60, 0.5 ⁇ c ⁇ 5, 0 ⁇ d ⁇ 10.
  • a Cu-base amorphous alloy comprising an amorphous phase of 90% or more by volume fraction.
  • the amorphous phase has a composition represented by the following formula:
  • M is one or more elements selected from the group consisting of Fe, Cr, Mn, Ni, Co, Nb, Mo, W, Sn, Al, Ta and rare earth elements
  • T is one or more elements selected from the group consisting of Ag, Pd, Pt and Au
  • a, b, c and d are atomic percentages falling within the following ranges: 10 ⁇ a ⁇ 40, 5 ⁇ b ⁇ 30, 35 ⁇ a+b ⁇ 50, 0.5 ⁇ c ⁇ 5, 0 ⁇ d ⁇ 10.
  • the above Cu-base amorphous alloys of the present invention may have a supercooled liquid region with a temperature interval ⁇ Tx of 25 K or more.
  • the Cu-base amorphous alloys of the present invention may have a reduced glass transition temperature of 0.56 or more.
  • the reduced glass transition temperature is represented by the following formula: Tg/Tm, wherein Tg is a glass transition temperature of the alloy, and Tm is a melting temperature of the alloy.
  • the Cu-base amorphous alloys of the present invention may be formed as a rod or plate material having a diameter or thickness of 1 mm or more and an amorphous phase of 90% or more by volume fraction, through a metal mold casting process.
  • the Cu-base amorphous alloys of the present invention may have a compressive fracture strength of 1800 MPa or more, an elongation of 1.5% or more, and a Young's modulus of 100 GPa or more.
  • the term “supercooled liquid region” herein is defined by the difference between a glass transition temperature of the alloy and a crystallization temperature (or an initiation temperature of crystallization) of the alloy, which are obtained from a differential scanning calorimetric analysis performed at a heating rate of 40 K/minute.
  • the “supercooled liquid temperature region” is a numerical value indicative of resistibility against crystallization which is equivalent to thermal stability of amorphous state, glass-forming ability or formability.
  • the alloys of the present invention have a supercooled liquid temperature region ⁇ Tx of 25 K or more.
  • the term “reduced glass transition temperature” herein is defined by a ratio of the glass transition temperature (Tg) to a melting temperature (Tm) of the alloy which is obtained from a differential scanning calorimetric analysis (DTA) performed at a heating rate of 5 K/minute.
  • the “reduced glass transition temperature” is a numerical value indicative of the glass-forming ability.
  • FIG. 1 is a graph showing a composition range of Cu-Zr-Ti ternary alloys capable of forming a bulk amorphous material and the critical thickness (unit: mm) of the bulk amorphous materials.
  • FIG. 2 is a graph showing a stress-strain curve in a compression test of a Cu 60 Zr 20 Ti 20 bulk amorphous alloy having a diameter of 2 mm.
  • Zr and/or Hf are basic elements for forming an amorphous material.
  • the content of Zr and/or Hf is set in the range of greater than 5 atomic % up to 55 atomic %, preferably in the range of 10 to 40 atomic %. If the content of Zr and/or Hf is reduced to 5 atomic % or less or increased to greater than 55 atomic %, the supercooled liquid region ⁇ Tx and the reduced glass transition temperature Tg/Tm will be reduced, resulting in deteriorated glass-forming ability.
  • Element Ti is effective to enhance the glass-forming ability to a large degree. However, if the content of Ti is increased to greater than 45 atomic %, the supercooled liquid region ⁇ Tx and the reduced glass transition temperature Tg/Tm will be reduced, resulting in deteriorated glass-forming ability. Thus, the content of Ti is set in the range of 0 to 45 atomic %, preferably 5 to 30 atomic %.
  • the total of the content of Zr and/or Hf and the content of Ti is set in the range of greater than 30 atomic % up to 60 atomic %. If the total content of these elements is reduced to 30 atomic % or increased to greater than 60 atomic %, the glass-forming ability will be deteriorated, and no bulk material can be obtained. Preferably, the total content is set in the range of 35 to 50 atomic %.
  • Cu of up to 10 atomic % may be substituted with one or more element selected from the group consisting of Ag, Pd, Au and Pt. This substitution can slightly increase the temperature interval of the supercooled liquid region. If greater than 10 atomic % of Cu is substituted, the supercooled liquid region will be reduced to less than 25 K, resulting in deteriorated glass-forming ability.
  • the glass-forming ability is deteriorated as the addition of these elements is increased.
  • the content of these element is preferably set in the range of 0.5 to 5 atomic %.
  • FIG. 1 shows a composition range of Cu-Zr-Ti ternary alloys capable of forming a bulk amorphous material and the critical thickness of the bulk amorphous materials.
  • the composition range capable of forming a bulk amorphous material (having a diameter of 1 mm or more) is shown by the solid line.
  • the numeral in the circle indicates the maximum thickness (unit:mm) of the bulk amorphous materials to be formed in the bulk amorphous materials.
  • FIG. 2 shows a stress-strain curve in a compression test of a Cu 60 Zr 20 Ti 20 bulk amorphous alloy. This alloy has a compressive fracture strength of about 2000 MPa, an elongation of 2.5%, and a Young's modulus of 122 GPa.
  • the Cu-base amorphous alloy of the present invention can be cooled and solidified from its molten state through various processes, such as a single-roll process, a twin-roll process, an in-rotating liquid spinning process and an atomization process, to provide an amorphous solid in various forms, such as thin strip, filament or powder/particle.
  • the Cu-base amorphous alloys of the present invention can also be formed as a bulk amorphous alloy having an arbitrary shape through not only the above conventional processes but also a process of filling a molten metal in a metal mold and casting therein by taking advantage of its high glass-forming ability.
  • a mother alloy prepared to have the alloy composition of the present invention is molten in a silica tube under argon atmosphere. Then, the molten alloy is filled in a copper mold at an injection pressure of 0.5 to 1.5 kg ⁇ f/cm 2 , and solidified so as to obtain an amorphous alloy ingot.
  • any other suitable method such as a die-casting process or a squeeze-casting process may be used.
  • a rod-shaped sample of 1 mm diameter was prepared for each of the above materials, and the amorphous phase in the rod-shaped sample was determined through an X-ray diffraction method.
  • the volume fraction (Vf-amo.) of the amorphous phase in the sample was also evaluated by comparing the calorific value of the sample during crystallization with that of a completely vitrified thin strip of about 20 ⁇ m thickness, by use of DSC. These evaluation results are shown in Table 1.
  • each of the amorphous alloys of Comparative Examples 1 and 2 in which the total of the content of Zr and/or Hf and the content of Ti is 30 atomic %, exhibited no glass transition, and no amorphous alloy rod of 1 mm diameter could be formed therefrom due to its poor glass-forming ability.
  • the amorphous alloy of Comparative Example 3 in which the content of Ni is 10 atomic %, exhibited no glass transition, and no amorphous alloy rod of 1 mm diameter could be formed therefrom due to its poor glass-forming ability.
  • each of the amorphous alloys of Inventive Examples exhibited a compressive fracture strength ( ⁇ f) of 1800 MPa or more, an elongation ( ⁇ ) of 1.5% or more, and a Young's modulus (E) of 100 GPa or more.
  • a rod-shaped sample having a diameter (thickness) of 1 mm or more can be readily prepared through a metal mold casting process.
  • the amorphous alloy exhibits a supercooled liquid region of 25 K or more, and has high strength and Young's modulus.
  • the present invention can provide a practically useful Cu-base amorphous alloy having a high glass-forming ability as well as excellent mechanical properties and formability.

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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)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
US10/451,143 2000-12-27 2001-11-28 Cu-base amorphous alloy Abandoned US20040112475A1 (en)

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JP2000397007 2000-12-27
JP2000-397007 2000-12-27
JP2001-262438 2001-08-30
JP2001262438A JP4011316B2 (ja) 2000-12-27 2001-08-30 Ｃｕ基非晶質合金
PCT/JP2001/010410 WO2002053791A1 (fr) 2000-12-27 2001-11-28 Alliage amorphe à base de cuivre

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Cited By (5)

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US20060231169A1 (en) * 2005-04-19 2006-10-19 Park Eun S Monolithic metallic glasses with enhanced ductility
US20070175550A1 (en) * 2003-06-17 2007-08-02 Korea Institute Of Science & Technology Method for producing composite materials comprising cu-based amorphous alloy and high fusion point element and composite materials produced by the method
US20080081213A1 (en) * 2006-09-28 2008-04-03 Fuji Xerox Co., Ltd. Amorphous alloy member, authenticity determining device, authenticity determination method, and process for manufacturing amorphous alloy member
US20160032435A1 (en) * 2014-07-30 2016-02-04 Apple Inc. Zirconium (zr) and hafnium (hf) based bmg alloys
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems

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US20070175550A1 (en) * 2003-06-17 2007-08-02 Korea Institute Of Science & Technology Method for producing composite materials comprising cu-based amorphous alloy and high fusion point element and composite materials produced by the method
US7591916B2 (en) * 2003-06-17 2009-09-22 Korea Institute Of Science & Technology Method for producing composite materials comprising Cu-based amorphous alloy and high fusion point element and composite materials produced by the method
US20060231169A1 (en) * 2005-04-19 2006-10-19 Park Eun S Monolithic metallic glasses with enhanced ductility
US7582173B2 (en) * 2005-04-19 2009-09-01 Yonsei University Monolithic metallic glasses with enhanced ductility
US20080081213A1 (en) * 2006-09-28 2008-04-03 Fuji Xerox Co., Ltd. Amorphous alloy member, authenticity determining device, authenticity determination method, and process for manufacturing amorphous alloy member
US8325987B2 (en) 2006-09-28 2012-12-04 Fuji Xerox Co., Ltd. Amorphous alloy member and its application for authenticity determining device and method, and process for manufacturing amorphous alloy member
US20160032435A1 (en) * 2014-07-30 2016-02-04 Apple Inc. Zirconium (zr) and hafnium (hf) based bmg alloys
US10280494B2 (en) * 2014-07-30 2019-05-07 Apple Inc. Zirconium (Zr) and Hafnium (Hf) based BMG alloys
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems
US11821064B2 (en) * 2019-04-30 2023-11-21 Oregon State University Cu-based bulk metallic glasses in the Cu—Zr—Hf—Al and related systems

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WO2002053791A1 (fr) 2002-07-11
JP2002256401A (ja) 2002-09-11
EP1354976A4 (en) 2009-04-29
EP1354976A1 (en) 2003-10-22
JP4011316B2 (ja) 2007-11-21
US8470103B2 (en) 2013-06-25
US20090078342A1 (en) 2009-03-26

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