A phosphorus-containing bulk zirconium-based amorphous alloy and a preparation method thereof

Abstract

This invention relates to the field of zirconium-based amorphous alloy preparation technology, specifically to a phosphorus-containing bulk zirconium-based amorphous alloy and its preparation method. The general formula for the composition of this zirconium-based amorphous alloy is: (Zr... a Cu b Al c M （100‑a‑b‑c） ) 100‑x P x Where 53.5≤a≤60, 25≤b≤33.3, 7.5≤c≤10, 0.35≤x≤0.6, and a, b, c, and x are atomic ratios, and M is one or more of Fe, Co, Ni, and Nb. Phosphorus is introduced into the alloy in the form of a copper-phosphorus alloy, resulting in an amorphous fraction greater than or equal to 80%. Adding phosphorus can significantly improve the gas efficaciousness (GFA) of the matrix alloy, increasing the critical diameter for amorphous formation from 3-5 mm to 8-14 mm, and the compressive fracture strength from 1.8 GPa to 2.4 GPa. The zirconium-based amorphous alloy has a large critical diameter for amorphous formation and good thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of zirconium-based amorphous alloy preparation technology, specifically relating to a phosphorus-containing bulk zirconium-based amorphous alloy and its preparation method. Background Technology

[0002] Amorphous alloys are a class of novel metallic materials with randomly arranged atoms, prepared by rapid cooling of high-temperature melts. With their core properties such as high strength, high hardness, and excellent corrosion resistance, they have shown great application potential in various high-end fields, including consumer electronics, biomedicine, and aerospace. Among them, zirconium-based amorphous alloys, with zirconium as the core component and supplemented by alloying elements such as Ti, Cu, Ni, Al, and Nb, have become one of the most engineering-valuable alloys in the amorphous alloy family due to their excellent glass-forming ability, comprehensive mechanical properties, and wide industrial processing window. Currently, zirconium-based amorphous alloys have achieved large-scale application in the consumer electronics field, especially as ideal materials for key structural components such as hinges, pivots, and card trays in foldable screen phones. They have been successfully applied in some mainstream brands of foldable screen models, and their high elastic limit and fatigue resistance provide crucial support for the reliability of foldable devices.

[0003] Despite the promising applications of zirconium-based amorphous alloys, current technologies still face multiple bottlenecks that severely restrict their industrialization: Firstly, the amorphous forming capability and critical size. Traditional zirconium-based amorphous alloys rely on extremely high critical cooling rates (typically as high as 10² to 10⁻⁶). 4 The use of K / s to suppress crystal nucleation and growth during the cooling process severely limits the critical size that can be prepared (most systems can only obtain samples in the millimeter to centimeter range), making it difficult to obtain large and complex components through conventional casting processes, thus limiting its application to micro-precision structural parts for a long time; secondly, the problem of intrinsic brittleness has not been effectively overcome. Amorphous alloys lack the dislocation slip mechanism of crystalline materials during room temperature deformation, and the deformation is highly localized within a narrow shear band, which easily leads to sudden brittle fracture. This defect seriously hinders its widespread application in load-bearing structural components.

[0004] Phosphorus, as a typical metalloid element, exhibits unique structural control capabilities in alloy systems. Its atomic radius differs significantly from that of zirconium, the main element in zirconium-based alloys. During solidification, it can fill the interatomic stacking gaps, increasing the random stacking density and thus widening the supercooled liquid phase region and reducing the critical cooling rate. Theoretically, this creates conditions for increasing the critical forming size. Simultaneously, phosphorus possesses high electronegativity, allowing it to form strong directional bonds with metals such as Zr, Cu, and Ni, including covalent components. This optimizes interatomic bonding forces and is expected to improve compressive strength while simultaneously increasing the critical size. Furthermore, phosphorus is abundant and inexpensive, offering significant economic advantages and engineering potential compared to precious metal or rare earth doping strategies.

[0005] However, existing research has not systematically elucidated the mechanism of phosphorus's role in zirconium-based amorphous alloys. Related studies on trace additions have mostly focused on traditional elements such as boron, silicon, and yttrium. Only a few studies have mentioned the potential impact of phosphorus on the soft magnetic properties and amorphous forming ability of Fe-based amorphous alloys, and the ductility and toughness of Ni-based amorphous alloys. No research has yet deeply focused on the functional regulation role of phosphorus in zirconium-based amorphous alloys, especially lacking a systematic exploration of phosphorus content, addition methods, and its interaction with the alloy's principal components. Of particular interest is the strong tendency for phosphorus to form compounds with zirconium. How to utilize its beneficial effects while avoiding excessive precipitation of brittle intermetallic compounds has become a crucial scientific problem that urgently needs to be solved.

[0006] To address this, this invention develops a novel zirconium-based amorphous alloy system with added phosphorus. By precisely controlling the phosphorus content and its synergistic ratio with the alloy's main components, a significant synergistic improvement in amorphous forming capability and mechanical properties is achieved for the first time, effectively overcoming the dual bottlenecks of critical size and core performance. This innovation not only provides an original technical path for developing novel zirconium-based amorphous alloys that combine large-size forming capability with excellent strength and toughness matching, but also has crucial practical significance and engineering value for promoting the expansion of zirconium-based amorphous alloys from micro-precision structural components to large load-bearing structural components and high-end functional devices. Summary of the Invention

[0007] To fill the gap in the application of phosphorus (P) in zirconium-based amorphous alloys, this invention discloses a phosphorus-containing blocky zirconium-based amorphous alloy and its preparation method. It innovatively employs a copper-phosphorus alloy to achieve precise phosphorus addition, avoiding the uneven distribution problem associated with single-element addition, and combines it with a portion of the zirconium-based amorphous alloy. By precisely controlling the phosphorus content, the amorphous forming ability and mechanical properties are significantly improved. Combined with a copper mold gravity casting process, it overcomes the bottlenecks in forming size and performance, significantly increasing the critical diameter while optimizing thermal stability. This provides theoretical support and assurance for engineering applications and has crucial practical significance for promoting the expansion of zirconium-based amorphous alloys into large structural components and high-end functional components.

[0008] The technical solution of this invention is: This invention discloses a phosphorus-containing bulk zirconium-based amorphous alloy, the general formula of which is: (Zr a Cu b Al c M （100-a-b-c） ) 100-x P xWhere 53.5≤a≤60, 25≤b≤33.3, 7.5≤c≤10, 0.35≤x≤0.6, and a, b, c, and x are atomic ratios, and M is one or more of Fe, Co, Ni, and Nb. Phosphorus is introduced into the alloy in the form of a copper-phosphorus alloy because phosphorus has a lower melting point than other metals. Direct addition would easily lead to volatilization and compositional deviation, while dissolving it in alloy form avoids this problem. The amorphous integral is ≥80%, the critical diameter for amorphous formation is increased from 3-5 mm to 8-14 mm, and the compressive fracture strength is increased from 1.8 GPa to 2.4 GPa.

[0009] Furthermore, in the aforementioned phosphorus-containing bulk zirconium-based amorphous alloy, the phosphorus content in the copper-phosphorus alloy is 12-16 wt.%, and the raw material purity is higher than 99%. Introducing phosphorus in the form of a copper-phosphorus alloy has two advantages: firstly, the pre-alloying properties allow for uniform dispersion of phosphorus in the matrix during high-temperature melting, effectively avoiding the problem of easy volatilization and compositional deviation caused by direct addition of elemental phosphorus; secondly, the phosphorus in the copper-phosphorus alloy can alter the melt environment through interaction with metal atoms. This dual effect allows the zirconium-based amorphous alloy to maintain its properties even at low vacuum levels (10⁻⁶ wt.%). -2 ~3.5×10 -3 Even under conditions of Pa, repeated casting can still maintain excellent glass-forming ability (GFA), providing a key stability guarantee for the large-scale and mass production of materials.

[0010] Furthermore, the total amount of non-metallic impurities in the aforementioned phosphorus-containing bulk zirconium-based amorphous alloy is ≤0.1at, and the total amount of metallic impurities is ≤1at.%.

[0011] Furthermore, in the aforementioned phosphorus-containing bulk zirconium-based amorphous alloy, the general formula of the zirconium-based amorphous alloy composition is: (Zr a Cu b Al c M （100-a-b-c） ) 100-x P x , where 55≤a≤57, 26.7≤b≤30, 7.5≤c≤10, 0.35≤x≤0.6, and a, b, c, and x are all atomic ratios.

[0012] This invention also discloses a method for preparing the above-mentioned phosphorus-containing bulk zirconium-based amorphous alloy, comprising the following steps: Grinding removes the oxide layer from the surface of the raw material; The polished raw material is first pre-soaked in petroleum ether for 10-15 minutes, then placed in anhydrous ethanol and ultrasonically cleaned for 30 minutes before being dried. First, evacuate the electric arc furnace to a vacuum level of 3.0 × 10⁻⁶. -3Pa, then high-purity argon gas is introduced to a vacuum of 45-60 kPa, followed by electric arc melting; If the alloy composition contains Nb, first melt the Zr and Nb master alloy, turn the master alloy over twice, and then add Cu, Ni, Al and other elements as well as copper-phosphorus alloy; if there is no Nb, place the alloy together in the melting furnace and turn it over no less than five times, with each melting time being 2-2.5 minutes. Once the alloy has completely melted, the crucible should be quickly tilted within 2 seconds to prevent solidification. Subsequently, the copper mold was cast in a stepped copper mold and then rapidly cooled. The copper mold was made of oxygen-free copper. The cooling rate is 60-100 K / s.

[0013] Finally, the sample was wet-cut using a diamond circular saw blade (coolant was sprayed while cutting), with a feed rate not exceeding 50 mm / min.

[0014] By adjusting the percentage of phosphorus atoms in the zirconium-based amorphous alloy, the critical diameter and thermal stability of the amorphous alloy can be improved. Therefore, by adjusting the proportions of various components and phosphorus content in the zirconium-based amorphous alloy to the range described in this invention, not only is the overall performance of the zirconium-based amorphous alloy not affected, but it is also highly beneficial to improving the amorphous forming ability of the amorphous alloy, which has important practical significance for the industrial production of this zirconium-based amorphous alloy material.

[0015] The advantages and beneficial effects of this invention are as follows: 1. The present invention incorporates trace amounts of phosphorus into the zirconium-based amorphous alloy, which can significantly suppress crystal nucleation and reduce the critical cooling rate; by precisely controlling the phosphorus content, the glass-forming ability is greatly improved.

[0016] 2. The zirconium-based bulk amorphous alloy prepared by this invention not only breaks through the technical bottleneck of large-size forming, but also simultaneously meets the functional requirements such as high hardness and high thermal stability. It provides theoretical support for research in the field of amorphous alloys and opens up space for its practical application, possessing important theoretical significance and broad market prospects.

[0017] 3. The present invention has significant advantages in terms of raw materials and processes: all materials used are industrial-grade raw materials, which are easy to obtain and have controllable costs; combined with electric arc melting and copper mold casting processes, the overall process has low energy consumption and simple operation, and can quickly achieve large-scale production, demonstrating outstanding economic efficiency and industrialization potential.

[0018] 4. Phosphorus itself has environmentally friendly and non-toxic properties. This invention uses this element for alloying, and the composition does not contain the toxic component Be, which fully complies with the current green manufacturing concept and sustainable development requirements, and provides a new direction for the research and development of environmentally friendly high-performance alloys. Attached Figure Description

[0019] Figure 1 The XRD diffraction patterns of the amorphous alloy of Example 1 and Comparative Example 1 are shown below. Figure 2 The XRD diffraction patterns of the amorphous alloys of Examples 3 and 4 and Comparative Example 2 are shown. Figure 3 The XRD diffraction patterns of the amorphous alloy in Example 5 and Comparative Example 3 are shown below. Figure 4 The XRD diffraction patterns are those of the amorphous alloy in Example 7 and Comparative Example 4. Detailed Implementation

[0020] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be used to limit the scope of the present invention.

[0021] Example 1 This embodiment illustrates the zirconium-based amorphous alloy (Zr) provided by the present invention. 53.5 Cu 33.3 Al 9.5 Ni 3.7 ) 100-x P x Preparation of x=0.6.

[0022] This embodiment uses industrial-grade pure metal raw materials, with Zr metal being sponge zirconium and phosphorus being added as a copper-phosphorus alloy with a mass fraction of 14%.

[0023] The method for preparing zirconium-based amorphous alloy in this embodiment uses electric arc melting and includes the following steps: Remove the oxide layer from the surface of the raw material: grind the metal surface to remove the oxide layer, pre-soak the raw material in petroleum ether for 15 minutes after removing the oxide layer, then put it in anhydrous ethanol and clean it by ultrasonic cleaning for 30 minutes, and then dry it.

[0024] Then, the dried raw materials are placed in a vacuum arc furnace, and the furnace is first evacuated to a vacuum level of 3.0 × 10⁻⁶. -3 Pa, then high-purity argon gas is introduced to a vacuum of 60 kPa. The process is repeated 5 times, 2 minutes each time, to fully melt and mix the zirconium-based amorphous alloy raw material. After cooling, the master alloy is obtained.

[0025] The aforementioned master alloy was placed in the copper crucible of the tilting casting equipment, and the electric arc furnace was first evacuated to a vacuum level of 3.0 × 10⁻⁶. -3 Pa, then fill with high-purity argon gas to a vacuum of 60 kPa, with each melting process taking 2 minutes.

[0026] After the alloy has completely melted, the crucible is quickly (within 2 seconds) tilted, and the molten alloy is poured under gravity into stepped copper molds of different diameters made of oxygen-free copper to cool and solidify, with a cooling rate of 90 K / s. The samples are then wet-cut using a diamond circular saw blade to obtain samples of different diameters.

[0027] Depend on Figure 1 Therefore, it is clear that after adding phosphorus, the critical diameter of alloy A is 12 mm, the content of metallic impurity elements is 0.7 at%, the content of non-metallic impurity elements is 0.05 at%, the amorphous integral is 94%, and the fracture strength is 2001 MPa.

[0028] Example 2 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy is (Zr... 53.5 Cu 33.3 Al 9.5 Ni 3.7 ) 100-x P x x=0.37. The difference between this example and Example 1 is the difference in phosphorus content.

[0029] The samples were wet-cut using a diamond circular saw blade to obtain samples of different diameters. In this embodiment, the critical diameter of alloy B was 14 mm, with a metallic impurity element content of 0.75 at%, a non-metallic impurity element content of 0.05 at%, an amorphous integral of 96%, and a fracture strength of 1985 MPa.

[0030] Comparative Example 1 This comparative example prepared a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy was Zr. 53.5 Cu 33.3 Al 9.5 Ni 3.7 .

[0031] Depend on Figure 1 Therefore, without the addition of phosphorus, the critical diameter for amorphous formation is 8 mm (a crystallization peak appears in the XRD diffraction pattern when the diameter is 10 mm), and the fracture strength is 1832 MPa. It can be seen that the critical diameter of Example 1 above after adding phosphorus is 12 mm, which is a significant improvement compared with this example, and the compressive fracture strength is also increased by about 170 MPa.

[0032] Example 3 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy is (Zr... 55 Cu 30 Al 10 Ni5) 100-x Px x=0.35.

[0033] The cooling rate during the rapid cooling phase was 93 K / s. The samples were wet-cut using a diamond circular saw blade to obtain samples of different diameters. Figure 2 Thus, in this embodiment, the critical diameter of alloy C is 8 mm, the content of metallic impurity elements is 0.74 at, the content of non-metallic impurity elements is 0.05 at, the amorphous integral is 95%, and the fracture strength is 2041 MPa.

[0034] Example 4 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 3, except that the composition of this zirconium-based amorphous alloy is (Zr... 55 Cu 30 Al 10 Ni5) 100-x P x x=0.6. The difference between this example and Example 3 is the difference in phosphorus content.

[0035] The samples were wet-cut using a diamond circular saw blade to obtain samples of different diameters. For example... Figure 2 In this embodiment, the critical diameter of alloy D is 9 mm, the content of metallic impurity elements is 0.75 at, the content of non-metallic impurity elements is 0.02 at, the amorphous integral is 96%, and the fracture strength is 2012 MPa.

[0036] Comparative Example 2 This comparative example prepared a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy was Zr. 55 Cu 30 Al 10 Ni5.

[0037] like Figure 2 Without the addition of phosphorus, its critical diameter for amorphous formation is 3 mm (a crystallization peak appears in the XRD diffraction pattern when the diameter is 5 mm), and its fracture strength is 1847 MPa. It can be seen that the critical diameters of Examples 3 and 4 above are 8 mm and 9 mm respectively after the addition of phosphorus, which is a significant improvement compared with this example, and the compressive fracture strength is also increased by about 160 MPa.

[0038] Example 5 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy is (Zr... 57 Cu 26.7 Al 7.5 Co 5.8 Nb3) 100-x P x x=0.4.

[0039] Then, the dried Zr and Nb are placed in a vacuum arc furnace, and the furnace is first evacuated to a vacuum level of 3.0 × 10⁻⁶. -3 Pa, then high-purity argon gas is introduced to a vacuum of 60 kPa. The process is repeated twice, each time for 2 minutes, to obtain a Zr-Nb master alloy. Then, the electric arc furnace is opened and Cu, Ni, Al and copper-phosphorus alloy are added and the process is repeated five times to fully melt and mix the zirconium-based amorphous alloy raw materials. After cooling, the master alloy is obtained.

[0040] The aforementioned master alloy was placed in the copper crucible of the tilting casting equipment, and the electric arc furnace was first evacuated to a vacuum level of 3.0 × 10⁻⁶. -3 Pa, then fill with high-purity argon gas to a vacuum of 60 kPa, with each melting process taking 2 minutes.

[0041] The copper mold was cast at 1650℃ with a cooling rate of 65K / s. Samples of different diameters were obtained by wet cutting with a diamond circular saw blade. Figure 3 In this embodiment, the critical diameter of alloy E is 11 mm, the content of metallic impurity elements is 0.5 at%, the content of non-metallic impurity elements is 0.03 at%, the amorphous integral is 98%, and the fracture strength is 1972 MPa.

[0042] Example 6 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 5, except that the composition of this zirconium-based amorphous alloy is (Zr... 57 Cu 26.7 Al 7.5 Co 5.8 Nb3) 100-x P x x=0.6. The difference between this example and Example 5 is the difference in phosphorus content.

[0043] The samples were wet-cut using a diamond circular saw blade to obtain samples of different diameters. In this embodiment, the critical diameter of alloy F was 12 mm, with a metallic impurity element content of 0.7 at%, a non-metallic impurity element content of 0.04 at%, an amorphous integral of 93%, and a fracture strength of 1989 MPa.

[0044] Comparative Example 3 This comparative example prepared a zirconium-based amorphous alloy according to the method described in Example 5, except that the composition of this zirconium-based amorphous alloy was Zr. 57 Cu 26.7 Al 7.5 Co 5.8 Nb3.

[0045] Under conditions without the addition of phosphorus, such as Figure 3Its critical diameter for amorphous formation is 5 mm (when the diameter is 8 mm, a crystallization peak appears in the XRD diffraction pattern), and its fracture strength is 1807 MPa. It can be seen that the critical diameter of Example 5 after adding phosphorus is 11 mm, which is a significant improvement compared with this example, and the fracture strength is also improved after adding phosphorus.

[0046] Example 7 This embodiment prepares a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy is (Zr... 60 Cu 25 Al 10 Fe5) 100-x P x x=0.6.

[0047] The rapid cooling stage involved a cooling rate of 85 K / s, and the samples were wet-cut using a diamond circular saw blade to obtain samples of different diameters. For example... Figure 4 In this embodiment, the critical diameter of alloy G is 8 mm, the content of metallic impurity elements is 1 at%, the content of non-metallic impurity elements is 0.05 at%, the amorphous integral is 95%, and the fracture strength is 2036 MPa.

[0048] Comparative Example 4 This comparative example prepared a zirconium-based amorphous alloy according to the method described in Example 1, except that the composition of this zirconium-based amorphous alloy was Zr. 60 Cu 25 Al 10 Fe5, under conditions without the addition of phosphorus, such as Figure 4 Its critical diameter for amorphous formation is 3 mm (when the diameter is 5 mm, a crystallization peak appears in the XRD diffraction pattern), and its fracture strength is 1869 MPa. However, after adding phosphorus in Example 7, the critical diameter was significantly increased to 8 mm, and the fracture strength increased from 1869 MPa to 2036 MPa.

[0049] Below are all the embodiments and the critical diameters of the corresponding original alloys.

[0050] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Original diameter 8mm 8mm 3mm 3mm 5mm 8mm 3mm Diameter after adding P 12mm 14mm 8mm 9mm 11mm 12mm 8mm Original fracture strength 1832MPa 1832MPa 1847MPa 1847MPa 1807MPa 1807MPa 1869MPa Strength after adding P 2001MPa 1985MPa 2041MPa 2012MPa 1972MPa 1989MPa 2036MPa

Claims

1. A phosphorus-containing bulk zirconium-based amorphous alloy, wherein the general formula of the zirconium-based amorphous alloy is: (Zr a Cu b Al c M （100-a-b-c） ) 100-x P x Where 53.5≤a≤60, 25≤b≤33.3, 7.5≤c≤10, 0.35≤x≤0.6, and a, b, c, and x are atomic ratios, and M is one or more of Fe, Co, Ni, and Nb; phosphorus is introduced into the alloy in the form of copper-phosphorus alloy, and the amorphous component in the resulting alloy is greater than or equal to 80%. The addition of phosphorus increases the critical diameter for amorphous formation from 3-5 mm to 8-14 mm, and the compressive fracture strength from 1.8 GPa to 2.4 GPa.

2. The phosphorus-containing bulk zirconium-based amorphous alloy according to claim 1, characterized in that, The purity of the raw materials is higher than 99%, and the phosphorus content in the copper-phosphorus alloy is 12-16 wt.%.

3. The phosphorus-containing bulk zirconium-based amorphous alloy according to claim 1, characterized in that, In the zirconium-based amorphous alloy, the total amount of non-metallic impurities is ≤0.1at, and the total amount of metallic impurities is ≤1at.%.

4. The phosphorus-containing bulk zirconium-based amorphous alloy according to claim 1, characterized in that, The general formula for the components is: (Zr a Cu b Al c M （100-a-b-c） ) 100-x P x , where 55≤a≤57, 26.7≤b≤30, 7.5≤c≤10, 0.35≤x≤0.6, and a, b, c, and x are all atomic ratios.

5. A method for preparing a phosphorus-containing bulk zirconium-based amorphous alloy according to any one of claims 1-4, characterized in that, Includes the following steps: Grinding removes the oxide layer from the surface of the raw material; The polished raw material is first pre-soaked in petroleum ether for 10-15 minutes, then placed in anhydrous ethanol and ultrasonically cleaned for 30 minutes before being dried. Place the raw materials into the electric arc furnace, then evacuate the furnace to a vacuum level of 3.0 × 10⁻⁶. -3 Pa, then high-purity argon gas is introduced to a vacuum of 45-60 kPa, followed by arc melting to obtain the master alloy; The master alloy is placed in a tilting casting equipment for melting. After the alloy is completely melted, the crucible is tilted within 2 seconds to prevent solidification. It was then rapidly cooled after being cast in a stepped copper mold. Finally, the sample was wet-cut using a diamond circular saw blade, with a feed rate not exceeding 50 mm / min.

6. The method for preparing the phosphorus-containing bulk zirconium-based amorphous alloy according to claim 5, characterized in that, During the electric arc melting process, if the alloy composition contains Nb, the Zr-Nb master alloy is melted first, the master alloy is turned over twice, and then Cu, Ni, Al and other elements as well as copper-phosphorus alloy are added; if there is no Nb, the alloy is placed together in the melting furnace and turned over no less than five times, with each melting time being 2-2.5 minutes.

7. The method for preparing the phosphorus-containing bulk zirconium-based amorphous alloy according to claim 5, characterized in that, The copper mold is made of oxygen-free copper, and the rapid cooling rate is 60-100 K / s.

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