WO2018107830A1 - Alliage amorphe en vrac à base de zirconium hautement plastique sans béryllium ni nickel, et son procédé de préparation - Google Patents

Alliage amorphe en vrac à base de zirconium hautement plastique sans béryllium ni nickel, et son procédé de préparation Download PDF

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Publication number
WO2018107830A1
WO2018107830A1 PCT/CN2017/101424 CN2017101424W WO2018107830A1 WO 2018107830 A1 WO2018107830 A1 WO 2018107830A1 CN 2017101424 W CN2017101424 W CN 2017101424W WO 2018107830 A1 WO2018107830 A1 WO 2018107830A1
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alloy
less
amorphous alloy
bulk amorphous
zirconium
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PCT/CN2017/101424
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English (en)
Chinese (zh)
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吕昭平
曹迪
王辉
吴渊
刘雄军
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北京科技大学
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Publication of WO2018107830A1 publication Critical patent/WO2018107830A1/fr

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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
    • C22C45/10—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
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

Definitions

  • the invention belongs to a bulk amorphous alloy, in particular to a high plasticity Zr-based bulk amorphous alloy which does not contain metal elements Be and Ni, and has a critical dimension of not less than 5 mm and a plastic deformation capacity of not less than 3%.
  • Amorphous alloys are metal materials that have emerged in recent years as a new generation of structural and functional applications. Different from the long-range ordered arrangement of atoms in traditional metal materials, the atoms of amorphous alloys are randomly arranged, do not have long-range order, and do not have defects such as grain boundaries and dislocations in their microstructure. Amorphous alloys exhibit excellent properties such as high strength, high hardness, high elastic limit, low modulus, and corrosion resistance that cannot be achieved by conventional crystalline alloys. In addition, the amorphous alloy exhibits a high viscous flow in the supercooled liquid region, exhibiting superplastic deformation characteristics. This property of the amorphous alloy enables it to be accurately press molded in the supercooled liquid region. These superior properties make amorphous alloys have broad application prospects in many fields.
  • the invention develops a high-plastic zirconium-based bulk amorphous alloy without nickel and nickel, and aims to remove not only the Be and Ni elements which have toxic side effects on the human body, but also has good biocompatibility and strong amorphous forming ability and The plastic deformation ability is good to obtain a good comprehensive effect of the amorphous alloy in terms of safety, processability and economy.
  • L is one or more of J or K
  • J is at least one of Mn, Co, Zn, Au, Ag, Pd, Pt, Cd, Ru, Re, Os, Ir
  • K is V, At least one of Ta, Nb, Cr, W, Mo, and Y.
  • the critical dimension of Zr 40 Hf 14 Cu 26 Fe 8 Al 12 alloy capable of forming bulk amorphous is not less than 5 mm, and Vickers hardness is not Below 551 Hv, the plastic strain is not less than 5%, and the width of the supercooled liquid region is not less than 91K.
  • Another object of the present invention is to provide a method for preparing the above alloy, which specifically comprises the following steps:
  • Step 1 The metal Zr, Hf, Cu, Fe, Al, Ag, Nb, Co having a purity of 99.0 wt% to 99.99 wt% is converted into mass according to the atomic percentage of the above expression;
  • Step 2 The surface of the raw material in the step 1 is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;
  • Step 3 The raw materials processed in the step 2 are stacked in a non-consumable vacuum electric arc furnace or a cold heading suspension furnace in the order of melting point for melting. After the mother alloy is sufficiently smelted uniformly, the alloy is suction-cast into water-cooled copper molds of different sizes using a vacuum suction casting apparatus to obtain an amorphous alloy material.
  • the alloy does not contain Be and Ni elements harmful to living organisms, and is excellent in biocompatibility.
  • the alloy has a strong amorphous forming ability, and the amorphous alloy prepared by the copper mold suction casting method has a critical dimension of not less than 5 mm, and can satisfy the dimensional requirements in the field of amorphous alloy processing.
  • the alloy has good plastic deformation ability, and the plastic strain at break is more than 3%, and the maximum is up to 18%.
  • the alloy has high hardness and its Vickers hardness is higher than 540 Hv.
  • the alloy has a wide temperature range of supercooled liquid phase, not less than 53K, and up to 92K, which is advantageous for superplastic forming.
  • Figure 1 is an XRD pattern of a Zr-Hf-Cu-Fe-Al bulk amorphous alloy prepared in Example 1 of the present invention
  • Figure 2 is a graph showing the compressive stress-strain curve of a Zr-Hf-Cu-Fe-Al bulk amorphous alloy prepared in Example 1 of the present invention.
  • Figure 3 is an XRD pattern of Zr-Hf-Cu-Fe-Al-L1 and Zr-Hf-Cu-Fe-Al-L2 bulk amorphous alloys prepared in Examples 2 and 3 of the present invention.
  • Figure 4 is a Vickers hardness of a Zr-Hf-Cu-Fe-Al-L1 bulk amorphous alloy prepared in Example 2 of the present invention.
  • Example 1 Preparation and properties of Zr-Hf-Cu-Fe-Al bulk amorphous alloy
  • An alloy of Zr 46 Hf 8 Cu 26 Fe 8 Al 12 , Zr 44 Hf 10 Cu 26 Fe 8 Al 12 , Zr 42 Hf 12 Cu 26 Fe 8 Al 12 and Zr 40 Hf 14 Cu 26 Fe 8 Al 12 was obtained.
  • the compressive stress-strain curve of the alloy is shown in Figure 2. It can be seen that the alloy does not immediately undergo catastrophic fracture after reaching the yield strength, but undergoes a plastic deformation (> 5%), wherein the Zr 40 Hf 14 Cu 26 Fe 8 Al 12 alloy has the largest plastic deformation ability. The plastic deformation before fracture reached 18%, indicating that the bulk amorphous alloy of the alloy system has good plastic deformation ability. See Table 1 for the relevant plastic deformation capability data.
  • Figure 3 shows the XRD pattern of a 5 mm sample of Zr a Hf b Cu 26 Fe 8 Al 12 L1 g alloy.
  • the XRD pattern of the 5 mm sample has only a typical diffuse scattering peak, indicating that the 5 mm alloy is amorphous.
  • the alloy has a strong amorphous forming ability.
  • the alloy composition was prepared as Zr 46 Cu 26 Fe 8 Al 12 Hf 6 Nb 1 Co 1 and Zr 38 Cu 26 Fe 8 Al 12 Hf 14 Nb 1 Ag 1 .
  • the XRD pattern of the 5 mm sample of Zr a Hf b Cu 26 Fe 8 Al 12 L2 g alloy in Example 3 is shown in Fig. 3, in which only the amorphous diffuse scattering peak is typical, indicating that the 5 mm alloy is amorphous phase, the alloy Has a strong amorphous forming ability.
  • Table 1 Composition, mechanical properties and thermodynamic parameters of a non-Be non-Ni high plasticity Zr-based bulk amorphous alloy of the present invention

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un alliage amorphe en vrac à base de zirconium hautement plastique sans béryllium ni nickel, et son procédé de préparation. L'alliage comprend les composants suivants (en pourcentage atomique) : Zr : 38-50 %, Hf : 2-15 %, Cu : 20-30 %, Fe : 5-10 %, Al : 10-15 %, Co : 0-5 %, Ag : 0-5 % et Nb : 0-5 % ; et l'alliage est préparé par moulage par aspiration dans un moule en cuivre/fusion à l'arc. L'alliage amorphe ne contient pas d'éléments métalliques tels que Be et Ni, améliorant ainsi la biocompatibilité de l'alliage à base de Zr ; l'alliage présente une capacité de formation amorphe élevée, ce qui permet la préparation d'un alliage amorphe en vrac à base de Zr ayant une taille critique non inférieure à 5 mm par un procédé de moulage par aspiration dans un moule en cuivre ; l'alliage présente une dureté élevée, sa dureté Vickers étant toujours supérieure à 540 Hv ; l'alliage présente une capacité de déformation plastique supérieure à 3 % ; et l'alliage présente une large plage de région liquide super-refroidie, le maximum étant de 92 K. Cet alliage présente de nombreuses possibilités d'application dans le domaine des pièces et des dispositifs médicaux complexes et précis, des articulations et des os artificiels, ainsi que dans d'autres matériaux biomédicaux.
PCT/CN2017/101424 2016-12-12 2017-09-12 Alliage amorphe en vrac à base de zirconium hautement plastique sans béryllium ni nickel, et son procédé de préparation WO2018107830A1 (fr)

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CN201611141148.2A CN106756647B (zh) 2016-12-12 2016-12-12 一种无铍无镍的高塑性锆基块体非晶合金及其制备方法
CN201611141148.2 2016-12-12

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CN115247243A (zh) * 2022-08-24 2022-10-28 盘星新型合金材料(常州)有限公司 含hf的轻质大尺寸块体非晶合金及其制备方法、应用
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

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CN106756647B (zh) * 2016-12-12 2019-06-11 北京科技大学 一种无铍无镍的高塑性锆基块体非晶合金及其制备方法
CN106702292B (zh) * 2016-12-12 2020-01-07 北京科技大学 含N的无Be无Ni高硬Zr基块体非晶合金及制备方法
CN107779790B (zh) * 2017-09-25 2019-04-19 北京科技大学 一种含锗无镍无磷大尺寸钯基非晶合金及其制备方法
CN108707844A (zh) * 2018-05-22 2018-10-26 大连理工大学 一种低成本Zr基块体金属玻璃及其制备方法
CN109182876B (zh) * 2018-10-19 2019-08-30 华中科技大学 一种晶态含铍高熵合金材料及其制备方法
CN109207872B (zh) * 2018-11-15 2020-12-29 北京科技大学 无镍无铍无铜高非晶形成能力的锆基块体非晶合金及制备
CN109355602B (zh) * 2018-11-15 2020-12-29 北京科技大学 具有高玻璃形成能力无镍无铍锆基非晶合金及制备和应用
CN109338252B (zh) * 2018-11-30 2020-11-06 昆明理工大学 一种锆基多孔非晶合金及制备方法
CN111363987B (zh) * 2020-03-26 2021-06-25 西安工业大学 一种超高初始晶化温度非晶合金及其制备方法
CN111996470A (zh) * 2020-08-26 2020-11-27 燕山大学 一种锆基大块非晶合金及其制备方法
CN113862585A (zh) * 2021-09-29 2021-12-31 盘星新型合金材料(常州)有限公司 多组分锆基大块非晶合金及其制备方法
CN114015953A (zh) * 2021-11-11 2022-02-08 盘星新型合金材料(常州)有限公司 无毒无镍的Zr基非晶合金及其制备方法
CN114606452B (zh) * 2022-02-25 2022-12-06 中国科学院宁波材料技术与工程研究所 一种高塑性Hf基双相非晶合金及其制备方法
CN114657480B (zh) * 2022-03-28 2023-04-28 北京科技大学 一种高塑性相分离Zr基非晶合金及其制备方法和应用

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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

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