EP2565289B1 - Wärmebehandlungsverfahren für einen druckguss aus einer amorphen legierung - Google Patents

Wärmebehandlungsverfahren für einen druckguss aus einer amorphen legierung Download PDF

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Publication number
EP2565289B1
EP2565289B1 EP11811855.3A EP11811855A EP2565289B1 EP 2565289 B1 EP2565289 B1 EP 2565289B1 EP 11811855 A EP11811855 A EP 11811855A EP 2565289 B1 EP2565289 B1 EP 2565289B1
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Prior art keywords
amorphous alloy
die cast
treatment process
heat treatment
alloy die
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EP11811855.3A
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English (en)
French (fr)
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EP2565289A4 (de
EP2565289A1 (de
Inventor
Yunchun Li
Faliang Zhang
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.)
BYD Co Ltd
Shenzhen BYD Auto R&D Co Ltd
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BYD Co Ltd
Shenzhen BYD Auto R&D Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • 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
    • C22C16/00—Alloys based on zirconium
    • 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
    • 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

Definitions

  • the present disclosure relates to methods of manufacturing amorphous alloys, more particularly to an amorphous alloy die cast and a heat treatment process of the same.
  • amorphous alloys possess a plurality of advantageous material properties that crystal metals do not have, such as better corrosion resistance, higher frictional resistance, and improved magnetic and electric properties.
  • Amorphous alloys are widely used in electronic, mechanical, chemical, and national defense industries.
  • bulk amorphous alloy also known as metallic glass
  • Bulk amorphous alloys usually are millimeter-sized.
  • bulk amorphous alloys are mainly prepared in research laboratories. Amorphous alloys may be prepared by several processes including melting and suction-casting process in an electrical arc furnace, solvent packaging process, water quenching process, or other processes.
  • Chinese Patent Application Publication No. CN101550521A discloses a rare-earth-based bulk amorphous alloy and its composite material.
  • the composite material is obtained based on the bulk amorphous alloy through a heat treatment process.
  • the heat treatment process includes an isothermal annealing of the rare-earth-based bulk amorphous alloy in a furnace at a temperature within the supercooled liquid region (325-650°C).
  • the process is performed in a 10 -3 Pa vacuum environment.
  • the composite material prepared thereof has improved thermal stability, higher electrical resistance, good soft magnetic property, and excellent processing capability in the supercooled liquid region.
  • this heat treatment process requires relatively high annealing temperature.
  • the temperature required must reside in the supercooled liquid region and is higher than the glass transition temperature Tg. Hence, the annealing process may cause portion of the amorphous alloy become crystallized.
  • the present disclosure aims to solve at least one of the foregoing problems, including the unstable properties of amorphous alloy obtained by die-casting techniques and complexity associated with known processes of bulk amorphous alloy preparation.
  • the present disclosure provides a novel heat treatment process of an amorphous alloy die cast as defined in claim 1.
  • the heat treatment process includes an aging treatment performed to the amorphous alloy die cast at a temperature of 0.5 Tg to 0.6 Tg for a time period of 10 minutes to 24 hours.
  • the amorphous alloy die cast is be prepared by a low-speed die casting process in a vacuum environment. The process is performed under a pressure of 50 Pascal (Pa) to 200 Pa, with a die casting speed of 3 meter per second (m/s) to 5 m/s.
  • the amorphous alloy die cast has a thickness of 0.5 millimeter (mm) to 2 mm.
  • the aging process is performed in a positive pressure of 0.1 MPa to 0.5 MPa.
  • the amorphous alloy die cast has a thickness of 1.0 mm to 1.5 mm.
  • the aging treatment is performed at a temperature of 0.53 Tg to 0.57 Tg, for a time period of 30 minutes to 60 minutes.
  • the amorphous alloy die cast comprises Zirconium (element Zr).
  • the Zirconium based amorphous alloy die cast is prepared by the heat treatment processes described above.
  • the Zirconium based amorphous alloy die cast is composed of (Zr 1-x Ti x ) a (Cu 1-y Ni y ) b Al c M d , wherein M is selected from the group consisting of: Be, Y, Sc, La, and combinations thereof; and 38 ⁇ a ⁇ 65, 0 ⁇ x ⁇ 0.45, 0 ⁇ y ⁇ 0.75, 20 ⁇ b ⁇ 40, 0 ⁇ c ⁇ 15, 0 ⁇ d ⁇ 30; and the sum of a, b, c, and d in atomic percentages equals to 100.
  • the amorphous alloy die cast obtained by the disclosed heat treatment process exhibits higher bending resistance and decreased property instability.
  • Traditional amorphous alloy die cast is usually not subjected to heat treatment.
  • gas in the die cast mold can be unavoidably trapped inside the die cast and form subsurface porosities. If the die cast is subsequently subjected to a heat treatment process, gas bubbles may be formed at the surface, causing deformation of the die cast. Hence, both the properties and the appearance of the die cast are negatively affected.
  • amorphous alloy In contrast to traditional Aluminum, Zinc, Magnesium or their combinational alloys, amorphous alloy has a low temperature supercooled liquid region.
  • the disclosed subject matter provides a novel process method that utilizes this supercooled liquid region to significantly reduce the gas trapped in the amorphous alloy comparing to that in the traditional metal alloys.
  • the disclosed subject matter provides a die casting process that is performed under a vacuum pressure of 50 Pa to 200 Pa, and at a low die casting speed of 3 m/s to 5 m/s.
  • risk of die cast bubbling during heat treatment may be effectively eliminated if the post die cast heat treatment is performed under atmospheric pressure or positive pressure, i.e., 0.1 Pa to 0.5 MPa, in the range of middle to high pressure.
  • the present invention discloses a novel heat treatment process of an amorphous alloy die cast.
  • the heat treatment process comprises two steps.
  • the first step comprises die casting and molding the amorphous alloy die cast at a pressure of 50 Pa to 200 Pa and at a die casting speed of 3m/s to 5m/s.
  • the resulted amorphous alloy die cast has a thickness ranging from 0.5 mm to 2 mm, with most of the die casts having thicknesses ranging from 1.0 mm to 1.5 mm.
  • the second step comprises performing an aging treatment on the amorphous alloy die cast, at a temperature of 0.5 Tg to 0.6 Tg, for a time period of 10 minutes to 24 hours.
  • Tg refers to the glass transition temperature measured in Kelvin.
  • a particular Tg of a certain amorphous alloy is obtained by DSC testing. DSC testing is a currently known technique.
  • the aging treatment is performed at atmospheric pressure or positive pressure. In some embodiments, a positive pressure of 0.1 MPa to 0.5 MPa is preferred in order to prohibit gas from diffusing to the surface of the die cast.
  • the preferred aging temperature is 0.53 Tg to 0.57 Tg and the preferred aging time period is 30 minutes to 60 minutes for a amorphous alloy die cast with a thickness of 1.0 mm to 1.5 mm.
  • the preferred aging treatment temperature may be increased or decreased; and the preferred heat treatment time period may be shortened or extended.
  • the aging treatment should be kept within 0.5Tg to 0.6Tg range.
  • the amorphous alloy die cast that is subjected to the above disclosed heat treatment process neither crystallizes, nor has gas bubbles at the surface.
  • the die cast exhibits improved material properties and enhanced stability. These improvements may be attributed to the following reasons.
  • the die cast is cooled off after molding. Cooling rates at different parts of the die cast are different. The different cooling rates may cause some weak areas or stress concentration regions.
  • the low aging treatment temperature ranging from 0.5 Tg to 0.6 Tg enables the relaxation and releasing of the concentrated stresses. Hence, the process disclosed in the present disclosure prevents the amorphous alloy die cast from premature fracturing before the material's yield point is reached. As a result, the material's performance and stability of the die cast are improved.
  • the amorphous alloy die cast is formed at a vacuum pressure of 50 Pa to 200 Pa and at a low casting speed of 3 m/s to 5m/s. Because the amorphous alloy has a high viscosity, the amount of gases trapped within the amorphous alloy die cast is less than that in the traditional alloy die casts. During subsequent aging treatment performed under middle to high pressure (about 0.1 MPa to 0.5 MPa), the positive pressure prohibits the trapped gas from diffusing to the surface of the amorphous alloy die cast.
  • the microstructure of the amorphous alloy is in a highly disordered and unstable state.
  • the low temperature aging treatment may not provide sufficient energy to overcome the energy barrier required for crystallization, it can overcome the metastable energy barrier and enable the transformation of the material structure from a high-energy long-range disordered state to a short-range ordered state.
  • the low temperature aging refers to aging treatment performed below the glass transition temperature. The current disclosure discloses that such a temperature range is from 0.5Tg to 0.6 Tg.
  • the alloy become, for example, pentagonal or dodecagonal quasicrystals, both have short-range ordered structures.
  • the short-range ordered structure cannot grow to become crystal, (the crystallization process requires re-melting into a disordered state), it can enhance the stability of the material properties.
  • the die cast after the aging treatment, the die cast exhibits an increased area under the crystallization peak. The increased area under the crystallization peak indicates more energy is released during the crystallization and in turn, indicates a more stable crystal structure and a more stable material property.
  • aging treatments were performed on two typical Zr-based amorphous alloys composed of Zr 55 Al 15 Cu 25 Ni 5 and Zr 41 Ti 14 Cu 15 Ni 10 Be 20 , respectively.
  • the two amorphous alloys have excellent glass forming ability, excellent mechanical properties and broad supercooled liquid region. Therefore, these two typical Zr-based alloys are selected to explain the effects of the aging treatment on the amorphous alloys.
  • high purity (purity is greater than 99.0wt%) Zr, Al, Cu, and Ni with a weight ratio corresponding to the composition of Zr 55 Al 15 Cu 25 Ni 5 were melted in an electrical arc furnace.
  • a copper mould was used for die casting in the presence of a protective Argon gas.
  • the die casting was performed in a condition of: a pressure of 150 Pa and a casting speed of 3m/s.
  • Fifteen amorphous alloy die casts were prepared for experimental purposes, each having a size of 80 mm ⁇ 6 mm ⁇ 1.5 mm.
  • the fifteen amorphous alloy die casts were labeled as A1 to A15, and having a composition of Zr 55 Al 15 Cu 25 Ni 5 .
  • the glass transition temperature Tg was determined to be 704K for this type of alloy by performing a DSC test.
  • the fifteen die casts were divided into three groups.
  • the first group includes A1 to A5, all of which were not subjected to any aging treatments.
  • the second group includes A6 to A10, each of which was subjected to an aging treatment in a pressure of 0.2 MPa, at a temperature of 0.53Tg (373K), for a time period of 1 hour.
  • the resulted die casts were labeled as B1 to B5.
  • the third group includes A11 to A15, each of which was subjected to an aging treatment in a pressure of 0.2 MPa, at a temperature of 0.81Tg (573K), for a time period of 1 hour.
  • the resulted die casts were labeled as C1 to C5.
  • X-ray powder diffraction analyses were performed on die cast samples A1, B1, and C1.
  • AD-MAX2200PC X-ray powder diffraction instrument was used, and the XRD analyses were performed under the following conditions: X-ray radiation was generated by a copper target; the incident wavelength ⁇ is1.54060 ⁇ ; the accelerating voltage is 40 KV; the current is 20 mA; and the scan step is 0.04°.
  • the XRD results are shown in Fig. 1 . It can be seen that A1 and B1 have amorphous structures and C1 has a crystal structure (the sharp diffraction peaks of C1 indicate a crystal structure).
  • high purity (purity is greater than 99.0wt%) Zr, Ti, Cu, Ni and Be with a weight ratio corresponding to the composition of Zr 41 Ti 14 Cu 15 Ni 10 Be 20 were melted in an electrical arc furnace.
  • a copper mould was used for die casting in the presence of a protective Argon gas.
  • the die casting was performed under a pressure of 120 Pa and with a casting speed of 4m/s.
  • Fifteen amorphous alloy die casts were prepared for experimental purposes, each having a size of 80 mm ⁇ 18 mm ⁇ 1 mm.
  • the fifteen amorphous alloy die casts were labeled as D1 to D15, and having a composition of Zr 41 Ti 14 Cu 15 Ni 10 Be 20 .
  • the glass transition temperature Tg was determined to be 662K for this type of alloy by performing a DSC test.
  • the fifteen die casts were divided into three groups.
  • the first group includes D1 to D5, all of which were not subjected to any aging treatments.
  • the second group includes D6 to D10, each of which was subjected to an aging treatment in an atmospheric pressure of 0.1 MPa, at a temperature of 0.57Tg (377K), for a time period of 0.5 hour.
  • the resulted die casts were labeled as E1 to E5.
  • the third group includes D11 to D15, each of which was subjected to an aging treatment under a pressure of 0.1 MPa, at a temperature of 0.47Tg (311K), for a time period of 0.5 hour.
  • the resulted die casts were labeled as F1 to F5.
  • die casts E1-E5 have improved bending resistance and stability, in comparison with die casts D1-D5, which were not subjected to any aging treatments, and die casts F1-F5, which were subjected to aging treatments under a temperature of 0.47Tg.
  • the terms “one embodiment,” “some embodiments,” “exemplary embodiment,” “specific exemplary embodiment,” or “some exemplary embodiments” mean that the described specific characteristics, structures, materials or features based on the underlining embodiments exist in at least one of the embodiments or exemplary embodiments. However, in this specification, an exemplary description associated with the above terms does not necessarily mean the same embodiment. In addition, the described specific characteristics, structures, materials or features may be properly combined in one or more embodiments or exemplary embodiments.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Claims (6)

  1. Wärmebehandlungsverfahren für einen Druckguss aus einer amorphen Legierung, umfassend das Unterwerfen des Druckgusses aus einer amorphen Legierung einer Alterungsbehandlung bei einer Temperatur von 0,5 Tg bis 0,6 Tg für eine Zeitspanne von 10 Minuten bis 24 Stunden; wobei Tg eine Glasübergangstemperatur der Legierung ist, wobei der Druckguss aus einer amorphen Legierung Zr umfasst und
    durch die Formel (Zr1-xTix)n(Cu1-yNiy)bAlcMd dargestellt ist, wobei
    M aus der Gruppe ausgewählt ist bestehend aus: Be, Y, Sc, La und Kombinationen davon,
    "x" im Bereich von 0 bis 0,45 in Atomprozent liegt,
    "y" im Bereich von 0 bis 0,75 in Atomprozent liegt,
    "a" im Bereich von 38-65 liegt,
    "b" im Bereich von 20-40 liegt,
    "c" im Bereich von 0 bis 15 liegt,
    "d" im Bereich von 0 bis 30 liegt und
    die Summe von a, b, c und d in Atomprozent gleich 100 ist.
  2. Wärmebehandlungsverfahren nach Anspruch 1, wobei der Druckguss aus einer amorphen Legierung durch ein Druckgießverfahren gebildet wird unter einer Bedingung von: einem Druck von 50 Pa bis 200 Pa und einer Druckgießgeschwindigkeit von 3 m/s bis 5 m/s.
  3. Wärmebehandlungsverfahren nach Anspruch 1 oder 2, wobei der Druckguss aus einer amorphen Legierung eine Dicke von 0,5 mm bis 2 mm aufweist.
  4. Wärmebehandlungsverfahren nach Anspruch 1, wobei die Alterungsbehandlung unter einem positiven Druck von 0,1 MPa bis 0,5 MPa ausgeführt wird.
  5. Wärmebehandlungsverfahren nach irgendeinem der Ansprüche 1-4, wobei die Temperatur 0,53 Tg bis 0,57 Tg beträgt und die Zeitspanne 30 Minuten bis 60 Minuten beträgt.
  6. Wärmebehandlungsverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei der Druckguss aus einer amorphen Legierung eine Dicke von 1 mm bis 1,5 mm aufweist.
EP11811855.3A 2010-07-29 2011-07-28 Wärmebehandlungsverfahren für einen druckguss aus einer amorphen legierung Active EP2565289B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010244468.7A CN102345082B (zh) 2010-07-29 2010-07-29 一种非晶合金压铸件及其热处理方法
PCT/CN2011/077762 WO2012013154A1 (zh) 2010-07-29 2011-07-28 一种非晶合金压铸件及其热处理方法

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EP2565289A4 EP2565289A4 (de) 2017-05-17
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EP2400353A1 (de) * 2010-06-22 2011-12-28 The Swatch Group Research and Development Ltd. Uhrenzeiger
ES2905448T3 (es) 2012-05-10 2022-04-08 Massachusetts Gen Hospital Métodos para determinar una secuencia nucleotídica
CN103774065A (zh) * 2012-10-19 2014-05-07 华为技术有限公司 一种锆基非晶合金
US9938605B1 (en) 2014-10-01 2018-04-10 Materion Corporation Methods for making zirconium based alloys and bulk metallic glasses
US10668529B1 (en) 2014-12-16 2020-06-02 Materion Corporation Systems and methods for processing bulk metallic glass articles using near net shape casting and thermoplastic forming
CN106282850A (zh) * 2015-05-18 2017-01-04 基准精密工业（惠州）有限公司 锆基非晶合金及其制备方法
CN109548765B (zh) * 2019-01-04 2024-01-02 鄱阳县黑金刚钓具有限责任公司 一种鱼钩及其制造方法
CN109609880B (zh) * 2019-01-29 2020-11-17 西安工业大学 一种含类金属的轻稀土基块体非晶合金及其制备方法
CN110295293A (zh) * 2019-06-28 2019-10-01 中国科学院金属研究所 一种非晶合金构件及其制备方法
CN111906271A (zh) * 2020-07-08 2020-11-10 松山湖材料实验室 用于谐波减速器非晶合金柔轮的真空压铸模具及其方法
CN112593123B (zh) * 2020-12-14 2021-11-09 昆明理工大学 一种锆基非晶颗粒增强铝基复合材料及其制备方法
CH718894A1 (fr) * 2021-08-02 2023-02-15 Hublot Sa Geneve Alliage à composition complexe.

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JPH09256122A (ja) * 1996-03-19 1997-09-30 Unitika Ltd Ｆｅ系非晶質合金
EP1632584A1 (de) * 2004-09-06 2006-03-08 Eidgenössische Technische Hochschule Zürich Amorphe Legierungen auf der Basis von Zr und deren Anwendung
CN101550521B (zh) 2008-04-01 2012-05-23 中国科学院物理研究所 具有磁热效应的稀土基块体非晶合金及其复合材料
CN101570837A (zh) * 2008-04-29 2009-11-04 比亚迪股份有限公司 一种锆基非晶合金及其制备方法

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CN102345082B (zh) 2017-02-22
US20120222785A1 (en) 2012-09-06
WO2012013154A1 (zh) 2012-02-02
EP2565289A4 (de) 2017-05-17
EP2565289A1 (de) 2013-03-06
CN102345082A (zh) 2012-02-08

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