EP0905268A1 - Hochfeste amorphe Legierung und Verfahren zu deren Herstellung - Google Patents

Hochfeste amorphe Legierung und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0905268A1
EP0905268A1 EP98111771A EP98111771A EP0905268A1 EP 0905268 A1 EP0905268 A1 EP 0905268A1 EP 98111771 A EP98111771 A EP 98111771A EP 98111771 A EP98111771 A EP 98111771A EP 0905268 A1 EP0905268 A1 EP 0905268A1
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EP
European Patent Office
Prior art keywords
phase
amorphous
alloy
strength
amorphous alloy
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EP98111771A
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English (en)
French (fr)
Inventor
Akihisa Inoue
Tao Zhang
Hidenobu Nagahama
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YKK Corp
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YKK Corp
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    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Definitions

  • the present invention relates to an amorphous alloy having high hardness and strength, excellent ductility, high corrosion resistance, and excellent workability, and a process for preparing the same.
  • a quenched tough thin strip formed by, for example, the liquid quenching method is heated at a temperature around the crystallization temperature thereof to precipitate crystals, the toughness thereof is deteriorated so that it can hardly be subjected to 180° contact bending.
  • the copper mold casting method a good amorphous bulk can be formed when cooled at a given or higher cooling rate, while the toughness thereof is deteriorated when the cooling rate is lowered to precipitate crystals.
  • the present invention aims at providing a high-strength amorphous alloy while solving the problem of deterioration of toughness either when a formed quenched tough thin strip or bulk material is heat-treated to precipitate crystals or when the cooling rate is lowered in the mold casting method to precipitate crystals.
  • the present invention provides a high-strength amorphous alloy represented by the general formula: X a M b Al c T d (wherein X is at least one element selected between Zr and Hf; M is at least one element selected from the group consisting of Ni, Cu, Fe, Co and Mn; T is at least one element having a negative enthalpy of mixing with at least one of the above-mentioned X, M and Al; and a, b, c and d are atomic percentages, provided that 25 ⁇ a ⁇ 85, 5 ⁇ b ⁇ 70, 0 ⁇ c ⁇ 35 and 0 ⁇ d ⁇ 15) and having a structure comprising at least an amorphous phase.
  • X is at least one element selected between Zr and Hf
  • M is at least one element selected from the group consisting of Ni, Cu, Fe, Co and Mn
  • T is at least one element having a negative enthalpy of mixing with at least one of the
  • the above-mentioned element T is at least one element selected from the group consisting of Ru, Os, Rh, Ir, Pd, Pt, V, Nb, Ta, Cr, Mo, W, Au, Ga, Ge, Re, Si, Sn and Ti, among which Pd, Pt and Au are especially effective.
  • the structure of the alloy of the present invention is a mixed phase comprising an amorphous phase and a microcrystalline phase.
  • the formation of the mixed phase structure provides excellent mechanical strength and ductility.
  • the amorphous phase preferably accounts for at least 50% in terms of volume fraction.
  • the present invention also provides a process for preparing a high-strength amorphous alloy, comprising preparing an amorphous alloy having a composition represented by the aforementioned general formula and containing at least an amorphous phase, and heat-treating the alloy in the temperature range from the glass transition temperature Tg thereof to the first exothermic reaction-starting temperature (Tx 1 : crystallization temperature) thereof to decompose the amorphous phase into a mixed phase structure consisting of an amorphous phase and a microcrystalline phase.
  • Tg glass transition temperature
  • Tx 1 crystallization temperature
  • the above-mentioned amorphous alloy can be prepared by quenching a molten alloy having the above-mentioned composition according to a liquid quenching method such as a single roller melt-spinning method, a twin roller melt-spinning method, an in-rotating-water melt-spinning method, a high-pressure gas atomizing method, or a spray method, by rapidly cooling it according to sputtering, or by slowly cooling it according to a mold casting method.
  • a liquid quenching method such as a single roller melt-spinning method, a twin roller melt-spinning method, an in-rotating-water melt-spinning method, a high-pressure gas atomizing method, or a spray method
  • the amorphous alloy thus obtained is heat-treated.
  • Tg heat-treated below Tg
  • Tx 1 the heat-treating temperature exceeds Tx 1
  • the crystalline phase formed by decomposition cannot be inhibited from coarsening. Accordingly, the structure can be stabilized by effecting the heat-treating in the range of Tg to Tx 1 .
  • the heating time may be 1 to 120 minutes. When it is shorter than 1 minute, no effect of heat-treating can be expected. When it exceeds 120 minutes, the crystalline phase is coarsened. This phenomenon is notably observed at a heat-treating temperature close to Tx 1 .
  • a mother alloy having the following composition: Zr 60 Cu 30-x Al 10 Pd x (wherein x 0, 5 or 10) (wherein the subscript refers to atomic %) was melted in an arc melting furnace, and then formed into a thin strip (thickness: 20 ⁇ m, width: 1.5 mm) with a single-roll liquid quenching unit (melt spinning unit) generally used. In this step, a roll made of copper and having a diameter of 200 mm was used at a number of revolutions of 4,000 rpm in an Ar atmosphere of not higher than 10 -3 Torr.
  • the glass transition temperature (Tg) and crystallization temperatures (Tx, Tx 1 and Tx 2 ) of each of the alloys (a) or (b) were as shown in the Figure.
  • the supercooled liquid region ( ⁇ T) is a region falling between the glass transition temperature (Tg) and each crystallization temperature (Tx, Tx 1 or Tx 2 ), a region where the control of temperature during working and the control of working time can be comparatively easily done, and a region serving as one of the criteria of whether or not working can be easily done.
  • the Tg refers to a temperature at a point of intersection of the extrapolated base line with the rising portion of the differential scanning calorimetric curve in a region of the curve where an endothermic reaction occurs
  • the Tx refers to a temperature found in the same manner in a region where an exothermic reaction occurs the other way around.
  • the alloy of the present invention is an alloy having a wide supercooled liquid region over 50 K in width as compared with the alloy of Comparative Example. It is also understood that the alloy of the present invention is an alloy having two exothermic peaks (Tx 1 , Tx 2 ).
  • Fig. 2 shows data on the X-ray diffraction analysis when the alloys (b) of Example as well as the alloy (a) of Comparative Example were heat-treated at a predetermined temperature for a predetermined period of time. It is understood that the alloy of Comparative Example underwent a considerable progress of crystallization by heat-treating in the supercooled liquid region at 705 K for 20 minutes. By contrast, it can be confirmed that the alloys of Example underwent no substantial change at 726 K in the supercooled liquid region for 30 minutes or 60 minutes, with a broad diffraction pattern peculiar to the amorphous phase. It can also be confirmed that the inventive alloys underwent a considerable progress of crystallization when heat-treated at 808 K above the supercooled liquid region, but still had a broad diffraction pattern as compared with the alloy of Comparative Example.
  • the alloy of the present invention is excellent in thermal stability and especially excellent in the properties in the supercooled liquid region Tg - Tx 1 .
  • Figs. 3A and 3B are the microstructural photographs (TEM, electron diffraction) of the alloy of Comparative Example when it was heat-treated in the supercooled liquid region for 40 minutes, from which it is understood that the crystal grains thereof were considerably coarsened as compared with those of Example of the present invention, which will be described later.
  • TEM electron diffraction
  • the alloys of Example were examined with respect to mechanical properties as against the volume fraction of the crystalline phase present in the matrix while varying the heat-treating time.
  • the heating temperature refers to a temperature in the supercooled liquid region.
  • the mechanical properties thereof such as tensile strength, hardness and Young's modulus were improved in keeping with an increase in the volume of the microcrystalline phase dispersed in the amorphous phase.
  • data at a volume fraction of 0 correspond to those of the alloys not heat-treated.
  • 180° contact bending test for every sample in Fig. 4 it was found out that all materials were capable of contact bending and were endowed with an excellent ductility.
  • the alloy of the present invention is a material endowed not only with an excellent thermal stability and excellent mechanical properties but also with an excellent ductility. Further, according to the process of the present invention, a material stabilized in structure and endowed with the foregoing properties can be prepared with proper control.

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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)
  • Continuous Casting (AREA)
EP98111771A 1997-08-29 1998-06-25 Hochfeste amorphe Legierung und Verfahren zu deren Herstellung Withdrawn EP0905268A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP247523/97 1997-08-29
JP9247523A JPH1171661A (ja) 1997-08-29 1997-08-29 高強度非晶質合金およびその製造方法

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EP0905268A1 true EP0905268A1 (de) 1999-03-31

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JP (1) JPH1171661A (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002027050A1 (en) * 2000-09-25 2002-04-04 Johns Hopkins University Alloy with metallic glass and quasi-crystalline properties
WO2002053791A1 (en) * 2000-12-27 2002-07-11 Japan Science And Technology Corporation Cu-base amorphous alloy
US6896750B2 (en) 2002-10-31 2005-05-24 Howmet Corporation Tantalum modified amorphous alloy
US6918973B2 (en) 2001-11-05 2005-07-19 Johns Hopkins University Alloy and method of producing the same
KR100701027B1 (ko) 2005-04-19 2007-03-29 연세대학교 산학협력단 연성이 우수한 단일상 비정질 합금
EP2881488A1 (de) 2013-12-06 2015-06-10 The Swatch Group Research and Development Ltd. Massive amorphe Legierung auf der Basis von Zirconium ohne Beryllium
CN104726801A (zh) * 2015-04-09 2015-06-24 中信戴卡股份有限公司 一种熔炼铝合金的方法及其制备的铝合金
US20160298217A1 (en) * 2015-04-09 2016-10-13 Citic Dicastal Co., Ltd Aluminum Alloy Refiner Material and Preparation Method Thereof
CN114164378A (zh) * 2021-12-01 2022-03-11 东莞市本润机器人科技股份有限公司 一种谐波减速器柔轮材料及其制备方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE530323C2 (sv) * 2006-09-26 2008-05-06 Foersvarets Materielverk Sätt att framställa föremål av amorf metall
JP4618569B2 (ja) * 2008-04-16 2011-01-26 独立行政法人科学技術振興機構 Ｃｕ基金属ガラス合金
WO2011159596A1 (en) 2010-06-14 2011-12-22 Crucible Intellectual Property, Llc Tin-containing amorphous alloy
CN104745973A (zh) * 2013-12-26 2015-07-01 比亚迪股份有限公司 一种锆基非晶合金及其制备方法
JP2021195569A (ja) * 2020-06-09 2021-12-27 株式会社Bmg ジルコニウム基金属ガラス合金
CN113981335B (zh) * 2021-10-29 2022-09-23 盘星新型合金材料(常州)有限公司 微量元素改性无Be块体非晶合金及其制备方法、应用
CN114836700B (zh) * 2022-06-15 2023-03-24 盘星新型合金材料(常州)有限公司 兼具高强度和高硬度的大尺寸锆基非晶合金及其制备方法
CN115637395A (zh) * 2022-09-19 2023-01-24 盘星新型合金材料(常州)有限公司 具有塑性变形的高硬度大尺寸锆基非晶合金及其制备方法
CN119640162B (zh) * 2024-12-26 2026-04-21 北京航空航天大学 一种Os基高温非晶合金材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0513654A1 (de) * 1991-05-15 1992-11-19 Tsuyoshi Masumoto Verfahren zur Herstellung von hochfestem Draht aus einer Legierung
JPH07188877A (ja) * 1993-12-28 1995-07-25 Takeshi Masumoto 生体用非晶質合金
JPH08199318A (ja) * 1995-01-25 1996-08-06 Res Dev Corp Of Japan 金型で鋳造成形された棒状又は筒状のＺｒ系非晶質合金及び製造方法
GB2310430A (en) * 1996-02-21 1997-08-27 California Inst Of Techn Quinary metallic glass alloys

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0513654A1 (de) * 1991-05-15 1992-11-19 Tsuyoshi Masumoto Verfahren zur Herstellung von hochfestem Draht aus einer Legierung
JPH07188877A (ja) * 1993-12-28 1995-07-25 Takeshi Masumoto 生体用非晶質合金
JPH08199318A (ja) * 1995-01-25 1996-08-06 Res Dev Corp Of Japan 金型で鋳造成形された棒状又は筒状のＺｒ系非晶質合金及び製造方法
GB2310430A (en) * 1996-02-21 1997-08-27 California Inst Of Techn Quinary metallic glass alloys

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
INOUE A ET AL: "Effect of additional elements on glass transition behavior and glass formation tendency of Zr-Al-Cu-Ni alloys", MATERIALS TRANSACTIONS, JIM, DEC. 1995, JAPAN INST. METALS, JAPAN, vol. 36, no. 12, ISSN 0916-1821, pages 1420 - 1426, XP002087478 *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 010 30 November 1995 (1995-11-30) *
PATENT ABSTRACTS OF JAPAN vol. 096, no. 012 26 December 1996 (1996-12-26) *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002027050A1 (en) * 2000-09-25 2002-04-04 Johns Hopkins University Alloy with metallic glass and quasi-crystalline properties
US6692590B2 (en) 2000-09-25 2004-02-17 Johns Hopkins University Alloy with metallic glass and quasi-crystalline properties
WO2002053791A1 (en) * 2000-12-27 2002-07-11 Japan Science And Technology Corporation Cu-base amorphous alloy
US6918973B2 (en) 2001-11-05 2005-07-19 Johns Hopkins University Alloy and method of producing the same
US6896750B2 (en) 2002-10-31 2005-05-24 Howmet Corporation Tantalum modified amorphous alloy
KR100701027B1 (ko) 2005-04-19 2007-03-29 연세대학교 산학협력단 연성이 우수한 단일상 비정질 합금
KR20150066473A (ko) * 2013-12-06 2015-06-16 더 스와치 그룹 리서치 앤 디벨롭먼트 엘티디 지르코늄계 및 베릴륨 프리 벌크 비정질 합금
WO2015082175A1 (fr) * 2013-12-06 2015-06-11 The Swatch Group Research And Development Ltd Alliage amorphe massif à base de zirconium sans béryllium
EP2881488A1 (de) 2013-12-06 2015-06-10 The Swatch Group Research and Development Ltd. Massive amorphe Legierung auf der Basis von Zirconium ohne Beryllium
KR101676122B1 (ko) 2013-12-06 2016-11-14 더 스와치 그룹 리서치 앤 디벨롭먼트 엘티디 지르코늄계 및 베릴륨 프리 벌크 비정질 합금
US9752218B2 (en) 2013-12-06 2017-09-05 The Swatch Group Research And Development Ltd Zirconium-based and beryllium free bulk amorphous alloy
US9890447B2 (en) 2013-12-06 2018-02-13 The Swatch Group Research And Development Ltd Zirconium-based and beryllium free solid amorphous alloy
CN104726801A (zh) * 2015-04-09 2015-06-24 中信戴卡股份有限公司 一种熔炼铝合金的方法及其制备的铝合金
US20160298217A1 (en) * 2015-04-09 2016-10-13 Citic Dicastal Co., Ltd Aluminum Alloy Refiner Material and Preparation Method Thereof
CN114164378A (zh) * 2021-12-01 2022-03-11 东莞市本润机器人科技股份有限公司 一种谐波减速器柔轮材料及其制备方法
CN114164378B (zh) * 2021-12-01 2022-06-03 东莞市本润机器人科技股份有限公司 一种谐波减速器柔轮材料及其制备方法

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